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A: Combustion and Plasma ChemistryJanuary 5, 2021

Near-Infrared Spectra of High-Density Crystalline H₂O Ices II, IV, V, VI, IX, and XII
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Christina M. Tonauer
Christina M. Tonauer
Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
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Eva-Maria Köck
Eva-Maria Köck
Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
Max-Planck-Institut für Chemische Energiekonversion, D-45470 Mülheim an der Ruhr, Germany
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http://orcid.org/0000-0002-4642-8315
Tobias M. Gasser
Tobias M. Gasser
Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
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Violeta Fuentes-Landete
Violeta Fuentes-Landete
Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
Max-Planck-Institut für Chemische Energiekonversion, D-45470 Mülheim an der Ruhr, Germany
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Raphael Henn
Raphael Henn
Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria
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Sophia Mayr
Sophia Mayr
Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria
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Christian G. Kirchler
Christian G. Kirchler
Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria
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Christian W. Huck
Christian W. Huck
Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria
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http://orcid.org/0000-0002-6272-3242
Thomas Loerting*
Thomas Loerting
Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
*Email: [email protected]
More by Thomas Loerting
http://orcid.org/0000-0001-6694-3843

Open PDF Supporting Information (9)

The Journal of Physical Chemistry A

Cite this: J. Phys. Chem. A 2021, 125, 4, 1062–1068

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https://doi.org/10.1021/acs.jpca.0c09764

Published January 5, 2021

Abstract

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High-pressure ice polymorphs are important for our understanding of hydrogen bonding and exist in the interior of the earth and icy moons. Nonetheless, spectroscopic information about them is scarce, where no information about their optical properties in the near-infrared (NIR) region is available at all. We here report NIR spectra of six ice polymorphs differing in terms of their density and O-atom topology, namely, ices II, IV, V, VI, IX, and XII, in comparison with the known spectra of ice I_h. By contrast to earlier work, we do not use mulling agents or transmission of thin films but use diffuse reflectance on powdered samples in liquid nitrogen. The first overtone of the OH-stretching mode is identified as the marker band most suitable to distinguish between these ices. There is a clear blue shift of this band that increases with increasing topological density in addition to a significant narrowing of the band.

Subjects

Introduction

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Water exhibits a fascinating range of solid phases termed ices. Hexagonal ice (ice I_h) is the most well-known form, appearing naturally on earth’s surface and in ice clouds. The first high-pressure ice polymorphs, ices II and III, were discovered more than 100 years ago by Tammann in the pressure range up to 0.4 GPa. (1−4) Extending the pressure range to 2 GPa, Bridgman discovered ices V and VI in the year 1912. (5) Ice IV appeared as a “ghostly form of ice,” (6) hard to make in a reproducible fashion, and so, it was assigned only in 1935. (7) Such ices do not occur naturally on earth’s crust since pressures in the interior of ice sheets and glaciers on the earth do not suffice to transform ice I_h to high-pressure polymorphs. Ice VI and ice VII do exist in earth’s mantle, though, as inclusions in superdeep diamonds, (8,9) formed in the mantle’s transition zone at depths of 410–660 km. (10) High-pressure ices also exist in the icy mantles of many moons in the Solar System. (11) They might also be present on the surface of icy bodies, such as the Jovian icy moons, through impact events or through transport from the interior to the surface. Once produced, they remain metastable for long times, provided the temperature remains below 150 K.

While all ice polymorphs have been characterized in terms of their crystal structures based on X-ray and/or neutron powder diffraction, spectroscopic information about ice phases is scarce. Only hexagonal ice is reasonably well characterized from the ultraviolet to the microwave part of the electromagnetic spectrum. (12,13) For high-pressure phases, barely any spectroscopic information is available, except for far- and mid-infrared spectra recorded by Whalley and co-workers in the 1960s. (14−17) Raman spectra were recorded by Minčeva-Śukarova and co-workers in the 1980s on ices II, III/IX, V, and VI (18,19) and by Mayer and co-workers in the early 2000s on ices IV, (20) XII/XIV, (21,22) and XIII. (23) Lately, also, Raman spectra of ices XV (24) and XIX (25) were reported. Since the pioneering IR spectroscopy studies on high-pressure ices by Whalley et al., more than 50 years have passed without any new spectra recorded. For none of the ices X–XIX discovered after the 1960s, spectra are available as of today neither in the far-, mid-, or near-infrared. Here, we provide near-infrared spectra of the six high-pressure polymorphs II, IV, V, VI, IX, and XII. These high-pressure ice phases differ in terms of density and the arrangement of oxygen atoms in the lattice. The increase of density compared to ice I_h is achieved through bending and compression of hydrogen bonds (ices II, IX), changes in the ring topology (ices V, XII), ring threading (ice IV), and interpenetration of two independent ice networks (ice VI). Thus, the choice of ice phases here allows us to see the impact of different hydrogen-bond patterns on the spectra of the ices. All spectra were recorded after recovery to ambient pressure under cryo-conditions (∼77 K) to avoid backconversion to stable ice I_h. Ice I_h serves as a reference and represents the only crystalline H₂O ice that has already been studied in literature in the NIR spectral range. (26−28)

Experimental Section

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Sample Preparation and X-Ray Diffraction (XRD) Characterization

High-pressure ices II, IV, V, VI, IX, and XII were prepared using a custom-made piston-cylinder setup described in former studies of the Innsbruck group. (29) In brief, 600 μL of ultrapure water in an indium container was loaded into the high-pressure cell and cooled to 77 K. Ices II, V, VI, and IX were prepared through isobaric heating of ice I_h at different pressures and from 77 K to different temperatures at different heating rates (18,30,31) (ice II: 0.3 GPa and 210 K at 2 K min^–1; ice V: 0.5 GPa and 250 K at 2 K min^–1; ice VI: 1.0 GPa and 255 K at >5 K min^–1; and ice IX: 0.5 GPa and 170 K at 3 K min^–1). Ices IV and XII were prepared through isobaric heating of unannealed high-density amorphous ice (uHDA) (32) at 0.8 GPa and 170 K at 0.4 K min^–1 and 180 K at >25 K min^–1, respectively. (20,21) Afterward, all samples were quenched to 77 K and recovered at ambient pressure. Before recording NIR spectra, the high-pressure samples were characterized by X-ray powder diffraction (Cu Kα₁ radiation; diffractometer, Siemens D5000 or Bruker D8 Advance), see Figure S1.

Near-Infrared Spectroscopy

All of the spectra presented here were recorded at ambient pressure and liquid nitrogen temperature (∼77 K). At these conditions, all of the ices are metastable with respect to ice I_h but can be kept indefinitely without the occurrence of any conversion. Ice III cannot be measured at 77 K because it converts to its hydrogen-ordered counterpart ice IX below 170 K. (33) Whalley and co-workers had devised a cryo-mulling technique and added isopentane to the ice samples to reduce the amount of ice in the optical path, enabling them to measure these ice samples in transmission geometry without black frequencies at the detector, that is, frequencies at which no transmitted light is detected. (34) By contrast, we here work on pure ice samples, without any mulling agent, and use a diffuse reflectance setup for the spectroscopic measurement. For spectroscopic characterization within the range of 10 000–4000 cm^–1 (1–2.5 μm), a Büchi NIR Flex N-500 benchtop spectrometer in diffuse reflectance mode was utilized. The high-pressure ice samples were powdered using a mortar under liquid nitrogen and transferred to a precooled quartz cuvette. In total, a layer of about 1 mm thickness was found to be sufficient to produce spectra with good signal-to-noise ratios. An optical cryo-microscopy image of such a powder is shown in Figure S2. Typical single grain diameters range from 15 to 40 μm. In addition to the single grains, larger aggregates of up to 350 μm are seen in the image. Then, the cuvette filled with the powdered sample and liquid nitrogen was placed in the optical path of the spectrometer. Due to the short acquisition time of a few seconds, the ice samples could be held at 77 K at all times during the experiment, preventing any undesired transitions. For each high-pressure ice, at least three independently prepared samples were analyzed, yielding at least 20 cumulative spectra per ice polymorph. Ice I_h was measured as a reference. Each cumulative spectrum was recorded within 16 s and represents a sum of 32 single spectra at resolution 8 cm^–1. That is, every spectrum shown in Figure 1 represents an average of 640 or more single spectra.

Figure 1. NIR spectra measured at ∼77 K (in blue), together with MIR spectra recorded in the 1960s and 1970s by Whalley and co-workers at ∼100 K from refs (14−16,35) (in gray). NIR spectra are normalized with respect to the band at ∼5000 cm^–1. Band assignments are given, where “x” means “unassigned”. Please note in (c) that Bertie and Whalley called the sample “ice III” even though it was measured at ∼100 K, that is, below the ordering temperature to ice IX.

Conversion of Spectra

The reflectance spectra were converted to Kubelka–Munk (K–M) function spectra, (36,37) according to eq 1

(1)

where F(R_∞) denotes the Kubelka–Munk or remission function, R_∞ is the reflectance of a layer sufficiently thick that transmission is negligible, and K and S are the absorption and scattering coefficients of the sample, respectively. Then, a baseline correction was applied by subtracting a basis spline constructed from eight anchor points (local minima of the K–M function) from the raw spectra. An example of such a baseline correction is shown in Figure S3. These single spectra were then normalized to a characteristic band and summed up. Finally, the sum spectra were normalized to the corresponding (global) maximum of the K–M function. To identify peak centers, we have not used a Gaussian decomposition procedure but rather employed first and second derivative spectra. Peak centers of the K–M function were identified as the zero crossings of the first derivative. Shoulders were identified through minima in the first derivative and zero crossings in the second derivative (see Figure S4).

Results and Discussion

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Figure 1 shows a summary of our spectra in the NIR range, together with the mid-infrared (MIR) spectra recorded by Whalley and co-workers. (14−16,35) The plot shows six high-pressure ice polymorphs and ice I_h, as discussed individually below.

Ice I_h is the only crystalline ice for which several NIR spectra are available at different temperatures. Rajaram et al. (38) and Warren and Brandt (13) provide the most recent reviews on measurements of optical constants of ice, all of which were done on thin films in transmittance. Leto et al. compared amorphous ice films with crystalline ice films in the range 1.33–2.50 μm (7500–4000 cm^–1) at 16–150 K. (28) The most comprehensive work is reported by Grundy and Schmitt, (27) who report transmission spectra in the range 20–270 K in the spectral range also investigated by us. To disentangle overlapping spectral features, they fit a number of Gaussians to each absorption band. As a result, Grundy and Schmitt identified 15 absorptions from 1.04 to 2.53 μm (9586–3960 cm^–1). However, they rightly point out that some Gaussians may not correspond to real vibrational modes but may be artifacts resulting from the fitting method. (27) In the same spectral range, we also identify 15 absorptions in diffuse reflectance, as seen in Figure 1a and listed in Table 1. Most of the features identified by Grundy and Schmitt are also identified by us directly, with the exception of the bands at 7256 cm^–1 (1.38 μm), 6579 cm^–1 (1.52 μm), and 6319 cm^–1 (1.58 μm). Furthermore, our spectral data exhibit more fine structure in the ν_OH + ν_R region, that is, the combination band of the OH-stretching ν_OH and the libration ν_R mode. We here recognize five sub-bands at 4034–4187 cm^–1 (2.48–2.39 μm), instead of just two.

Table 1. Near-Infrared (NIR) Bands of Ice I_h Measured in Diffuse Reflectance in Comparison with the Data by Grundy and Schmitt (27)^,^a

peak position (cm^–1)	peak position (μm)	assignment	Grundy and Schmitt (27) (cm^–1)	deviation (cm^–1)	deviation (μm)
9394	1.06	3ν_OH	9586 ± 40	192	–0.021

7888	1.27	2ν_OH + ν₂	7847 ± 10	–41	0.007
7656	1.31		7628 ± 3	–28	0.005
			7256 ± 50

6648	1.50	2ν_OH	6682 ± 5	34	–0.008
			6579 ± 10
6390	1.56		6403 ± 20	13	–0.003
			6319 ± 20
6050	1.65		6055 ± 1	5	–0.001

5600	1.79	ν_OH + ν₂ + ν_R	5565 ± 10	–35	0.011

4971	2.01	ν_OH + ν₂; ν_OH + 2ν_R	4983 ± 20	12	–0.005
4879	2.05		4948 ± 20	69	–0.029
4851	2.06		4837 ± 20	–14	0.006

4187	2.39	ν_OH + ν_R	4239 ± 5	52	–0.029
4145	2.41
4107	2.43
4066	2.46
4034	2.48
			3960 ± 5

^{^a}

Bands measured by G&S refer to a temperature of 80 K. Our bands were measured at 77 K.

Considering the ν_OH + 2ν_R combination band between 4971 and 4851 cm^–1, our results agree well with the ones published by Grundy and Schmitt. (27) As pointed out by Ockman, (39) this range also contains the ν_OH + ν₂ combination band, where ν₂ represents the bending mode. Grundy and Schmitt assume the weak feature at 5600 cm^–1 to be an artifact resulting from Gaussian decomposition, but we here assign it to combination band ν_OH + ν₂ + ν_R. Comparing the strong and sharp low-frequency contribution to the first overtone 2ν_OH at 6050 cm^–1, our result and the one of Grundy and Schmitt coincide within 5 cm^–1. In total, we recognize three sub-bands for 2ν_OH, 6050 cm^–1 (1.65 μm), 6390 cm^–1 (1.56 μm), and 6648 cm^–1 (1.50 μm) (see Table 1). Above 7000 cm^–1, we identify three bands at 7656, 7888 cm^–1, and 9394 cm^–1, which represent combination 2ν_OH + ν₂ and second overtone 3ν_OH. (39,40) That is, even at the upper and lower boundaries of the spectral range, all bands agree to better than 0.03 μm with the data by Grundy and Schmitt (see Table 1). This demonstrates that our procedure of defining the baseline and evaluating the Kubelka–Munk function (see Experimental Section) does not produce artifacts and that our spectra of powdered samples collected in diffuse reflectance mode compare in an excellent way with literature spectra obtained from thin films in transmission mode. One major advantage of the diffuse reflectance setup is that we do not need to worry about producing films of an appropriate thickness, suited for the absorptivities of the specific bands. Specifically, we do not need to make very thin samples for strong signals such as 2ν_OH and very thick samples for weak signals such as 3ν_OH. Instead, we only need to make sure that enough powder is loaded to prevent the incoming beam from transmitting the sample. This testifies that the spectra reported in the following for high-pressure ice polymorphs represent reliable spectroscopic information.

For the high-pressure polymorphs, no NIR data are available so far, with the exceptions of ice VI and ice VII. Larsen and Williams scrutinized the overtone spectrum of stretching and bending vibrations in H₂O and D₂O up to pressures of 37 GPa at 300 K. (41) Kagi et al. investigated ices VI and VII as an inclusion in a cuboid diamond in the range of 4500–5500 cm^–1. (8) The identification of the ice NIR spectra in that study has proven to be difficult because of the spectroscopic signatures of the diamond itself and signatures from other inclusions, such as liquid water, masking the ice bands. By contrast, we here report the ice VI spectra of the pure substance at 77 K and ambient pressure (solely minor impurities of ice XII in ice IV could not be avoided—see Figure S1b). Figure 1b–g shows the spectra of six high-pressure polymorphs. All of them have quite different oxygen atom networks. Two belong to the trigonal crystal system, namely, ice II (space group R-3) and ice IV (R-3c); three are tetragonal, ice VI (P42/nmc), ice IX (P4₁2₁2), and ice XII (I-42d); and one is monoclinic, ice V (C2/c). The latter has 28 molecules in its unit cell, whereas hexagonal ice has only 4. The other five high-pressure polymorphs have 10 (ice VI), 12 (ices II, IX, XII), and 16 (ice IV) water molecules per unit cell. While ice II and ice IX feature hydrogen order, ices IV, V, VI, and XII are hydrogen-disordered. Table 2 summarizes the NIR bands for the high-pressure polymorphs identified in this work.

Table 2. Near-Infrared (NIR) Bands for High-Pressure Ices Measured in Diffuse Reflectance at 77 K

peak position (cm^–1)
ice II	ice IX	ice IV	ice V	ice VI	ice XII
3ν_OH
9691	9657	9725			9690
2ν_OH + ν₂
8130	7974	8153	8083	8252	8058
8079	7785	8130	8043	8135
8049	7726	8113		8088
8006		8055		8034
2ν_OH + ν_R
7534	7264	7346	7254	7352	7269
7404	7190	7250		7248
7255
2ν_OH
6772	6724	6774	6746	6725	6768
6664	6690	6353	6716	6310	6740
6624	6648	6324	6648		6697
6346	6620	6296	6311		6659
6291	6562		6281		6628
6216	6180		6253		6365
					6351
					6325
not assigned
					6067
ν_OH + ν₂ + ν_R
5579	5564	5572	5522	5506	5534
	5553			5488	5503
					5400
ν_OH + ν₂, ν_OH + 2ν_R
5079	5034	5050	5043	5071	5049
5043	5019				5026
4948	4990				4991
4921	4952				4940
ν_OH + ν_R
4209	4196	4176	4191	4178	4206
4180	4162	4116	4158	4154	4161
4131	4132	4028	4118	4135	4144
4051	4107		4075	4096	4099
4020	4068		4048	4048	4044
	4045		4019		4025

We are able to resolve eight different types of combination bands and overtones that are labeled in Table 2. In total, 24 individual bands can be identified for ices II and IX but only 16 or 17 for ices IV, V, and VI (see Table 2). This is not surprising since sharper features are expected for H-ordered ices II and IX than for H-disordered ices IV, V, and VI. However, H-disordered ice XII is an exception to the rule—it shows 25 bands. This is probably related to its complex O-atom network, involving only large seven- and eight-membered rings, whereas all other ices studied here feature smaller four-, five-, or six-membered rings. (42) In general, all high-pressure polymorphs show three intense features, just like hexagonal ice. These are 2ν_OH, ν_OH + ν₂/ν_OH + 2ν_R, and ν_OH + ν_R and bands centered at about 6500, 5000, and 4100 cm^–1. In addition, the feature near 5500 cm^–1 is much more pronounced in all spectra of high-pressure ices than in hexagonal ice. We tentatively assign this band to the ν_OH+ν₂+ν_R combination mode. We also identify weak second overtone 3ν_OH but refrain from assigning it in ices V and VI because it is close to the noise level.

Figure 2a focuses on the 2ν_OH band, which is the most suitable marker band to clearly distinguish all high-pressure ices. Ice I_h exhibits a sharp feature at 1.65 μm (6050 cm^–1). It is used in remote sensing techniques to identify ice I_h in astrophysical environments (43) as well as a temperature probe (28) due to its strong temperature dependence. (27) At 77 K, it is a very prominent and rather intense feature only for ice I_h but appears as a shoulder for all H-disordered high-pressure ices (ices IV, V, VI, and XII) highlighted by diamonds in Figure 2a. In the case of H-ordered ice IX, this feature is also intense, and in the case of H-ordered ice II, this feature splits into three sharp subpeaks. These splittings can only be observed on the overtone of the OH-stretching mode but not on the fundamental vibration in the MIR of ice II (see Figure 1b). The doubling in frequencies in the first overtone compared to the fundamental vibration allows for a better separation of sub-bands, resolving features in the NIR that remain hidden in the MIR. For this reason, the NIR spectra presented here with their high signal-to-noise ratio and high resolution are better suited to distinguish between high-pressure polymorphs than the literature spectra in the MIR range. Yet another feature that distinguishes all high-pressure ices from ice I_h is the ν_OH + ν₂ + ν_R wing centered near 5500 cm^–1. As seen in Figure 2b, this wing is only very weak in ice I_h but of medium intensity in all high-pressure ices.

Figure 2. Comparison of the NIR features at (a) 6600 cm^–1 and (b) 5000 cm ^–1. (c–f) Correlation plots: (c) mass density and peak position, (d) mass density and full width at one-third of the maximum (FWTM), (e) topological density and peak position, and (f) topological density and FWTM. Filled diamonds in (c) and (e) correspond to the ones shown in (a). Open symbols in (c) and (e) represent sub-bands as extracted using the procedure shown in Figure S4.

It is immediately evident that all bands from high-pressure ices are blue-shifted compared to those from hexagonal ice (see Figure 2a,b). For example, the blue shift of the 6648 cm^–1 band in ice I_h amounts to about +100 cm^–1 for all ices, where ice IV is blue-shifted the most to 6774 cm^–1. Also, the 6050 cm^–1 feature (1.65 μm) described above is blue-shifted between 130 cm^–1 for ice IX and ∼300 cm^–1 for ice XII. The blue shift on this feature correlates quite well with the ambient pressure density of the ice polymorphs. Figure 2c shows a plot of the location of this feature versus the density of the high-pressure ice as determined by cryoflotation. (44) The trend is the denser the ice, the more blue-shifted the band, as indicated through the line guiding the eye in Figure 2c. Ice XII is an exception to this rule and shows the largest blue shift, even though ices IV and VI are slightly denser than ice XII. Figure 2e uses the topological density (relative to ice I_h) as defined by Herrero and Ramirez (Table 3 in ref (45)). Although ices IV and XII have a lower density compared to ice VI, they show a higher topological density. This improves the correlation with NIR spectra greatly.

Significant differences between the high-pressure polymorphs can be noted when inspecting the full width at one-third of the maximum (FWTM) for the intense “6600 cm^–1” and “5000 cm^–1” bands (see Table 3 and Figure 2d,f). Compared to ice I_h the FWTM is smaller for all high-pressure ices by up to 20%. Similar to the absolute position of the 6050 cm^–1 feature, there is a weak correlation of the FWTM with density (Figure 2d)—the higher the density, the smaller the FWTM. In terms of topological density (Figure 2f), there is no clear correlation. Ice VI exhibits the narrowest bands, and ice I_h shows the broadest ones. The density correlation is, however, not strict. Ices V and XII exhibit broader bands than expected according to their density; ice V even shows broader bands than ices II and IX. This is possibly related to the H-ordered nature of the latter two and the H-disordered of the former. That is, to make a good correlation plot, not only density needs to be considered but also the H-order. This requires future work and more data on H-ordered ices, e.g., ices XIII, XIV, XV, and XIX.

Table 3. Full Width at One-Third of the Maximum (FWTM) of the 2ν_OH and ν_OH + ν₂/ν_OH + 2ν_R Bands

	2ν_OH		ν_OH + ν₂/ν_OH + 2ν_R
	band maximum (cm^–1)	FWTM (cm^–1)	band maximum (cm^–1)	FWTM (cm^–1)
ice I_h	6648	943	4971	648
ice II	6772	806	5079	566
ice IX	6724	828	5019	565
ice IV	6774	760	5050	531
ice V	6746	835	5043	579
ice VI	6725	746	5071	530
ice XII	6697	801	5049	569

Conclusions

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In summary, we here report NIR spectra of six high-pressure ices ranging from densities of 1.16–1.34 g cm^–3, which is about 25–45% denser than ice I_h, the only ice polymorph for which NIR spectra have been available prior to our work. The increased density causes a strong blue shift of the overtones and combination bands compared to ice I_h. Also, the width of the bands is strongly reduced as the density increases. As a result, the sharp and strong feature useful to characterize ice I_h at 1.65 μm develops into a shoulder. Only for ices that are H-ordered, this sharp feature is retained, as in ice IX, or even split into several features, as in ice II. Yet, this band, the first overtone of the OH-stretching mode, is characteristic of these ices and can be used to identify the polymorphs. Tables 2 and 3 summarize the bands observed in our work, and Figure 1 compares our NIR spectra directly with MIR spectra obtained in pioneering works (14−17) (where ice XII is still lacking MIR data). Our attempts to extract anharmonicity from a comparison between the fundamental modes and the overtones/combination bands have been unsuccessful, especially because all of the bands are very broad, featuring severe coupling of modes and several subpeaks. Such attempts might be more successful for H-ordered ices, which are the focus of our ongoing work on NIR spectra of H₂O polymorphs. All spectra recorded in this work are also provided in the electronic form in the Supporting Material.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c09764.

Powder X-ray diffractograms of each high-pressure ice sample used in the present study; optical microscopy image of a powdered sample of hexagonal ice I_h at 248 K; depiction of the baseline correction procedure deployed; and peak identification based on first and second derivative spectra (PDF)
Normalized Kubelka–Munk function in % for ices I_h, II, IV, V, VI, IX, and XII is shown in Figures 1 and 2a,b (TXT)
Raw Kubelka–Munk function spectra of ice I_h (TXT)
Raw Kubelka–Munk function spectra of ice II (TXT)
Raw Kubelka–Munk function spectra of ice IV (TXT)
Raw Kubelka–Munk function spectra of ice V (TXT)
Raw Kubelka–Munk function spectra of ice VI (TXT)
Raw Kubelka–Munk function spectra of ice IX (TXT)
Raw Kubelka–Munk function spectra of ice XII (TXT)

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Author Information

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Corresponding Author
- Thomas Loerting - Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria; http://orcid.org/0000-0001-6694-3843; Email: [email protected]
Authors
- Christina M. Tonauer - Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
- Eva-Maria Köck - Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria; Max-Planck-Institut für Chemische Energiekonversion, D-45470 Mülheim an der Ruhr, Germany; http://orcid.org/0000-0002-4642-8315
- Tobias M. Gasser - Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
- Violeta Fuentes-Landete - Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria; Max-Planck-Institut für Chemische Energiekonversion, D-45470 Mülheim an der Ruhr, Germany
- Raphael Henn - Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria
- Sophia Mayr - Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria
- Christian G. Kirchler - Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria
- Christian W. Huck - Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck, A-6020 Innsbruck, Austria; http://orcid.org/0000-0002-6272-3242
Notes
The authors declare no competing financial interest.

Acknowledgments

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The authors thank Astrid Hauptmann and Alexander Thoeny for experimental help. The authors are grateful to the Center for Molecular Water Sciences Hamburg (CMWS) and the Austrian Science Fund (FWF) for support under the bilateral grant I1392. V.F.-L. and E.-M.K. are grateful to the Max Planck Institute for Chemical Energy Conversion for the financial support, and C.M.T. is a recipient of a DOC fellowship of the Austrian Academy of Sciences ÖAW.

References

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This article references 45 other publications.

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The Relation of the p-v and p-t Curves for Water to its Polymerization
Tammann, G.
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T. believes that the irregularities in the p-v and p-t curves for water between -20° and -80° and 1 kg. per sq. cm. and 12500 kg. per sq. cm. (data of Bridgman) are due to changes in the mol. species, which have different thermodynamic properties. The changes in species are the results of polymerization of the water.
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Tammann, G. On the State Diagram of Water. Z. Phys. Chem. 1913, 84, 257– 292, DOI: 10.1515/zpch-1913-8418
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The Diagram of State of Water
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(1913), 84 (), 257 ISSN:.
In this paper T. compares the recent data of Bridgman on the thermodynamic properties of water with his own, some of which he has redetd. for the occasion. Using this data, he works out anew the equil. curves between the various phases which are possible in the 1 component system between 0° and -60° and 2000 to 3000 kg per sq. cm.
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Tammann, G. The Behaviour of Water at High Pressure and Low Temperatures. Z. Phys. Chem. 1910, 72, 609– 631, DOI: 10.1515/zpch-1910-7232
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The Behavior of Water at High Pressures and Low Temperatures
Tammann, G.
(1910), 72 (), 609-31 ISSN:.
Water at temps. below 0° exists in several forms which fall into two groups: (a) those which are lighter and (b) those which are heavier than liquid H2O. (a) ordinary hexagonal ice I, absolutely stable at pressures less than 2200, atm.; and the unstable forms: the tetragonal ice observed by Nordenskiold, the regular crystals described by Barendrecht, and ice IV discovered by the author; the last may be identical with one of the other two. (b) Ice III (cf. C. A., 4, 1415) and the less stable ice II. These can be realized at ordinary pressure below -130°. A triple point is exhibited by the system ice III - ice 1 - H2O at -22° and 2200 kg. per sq. cm.; by the system ice II - ice I - H2O at - 22.4° and 2230 kg. Diagrams are given which illustrate equilibrium conditions throughout the field. From the conditions under which the different forms are observed, the conclusion is reached that the varieties of group (a) form only from H2O rich in polymolecules, while ice II and III form only from H2O consisting mainly of simple mols. or by compressing ice I to such an extent that the polymolecules are no longer stable. On this view the forms belonging to group (a) are made up of associated mols., while those of group (b) are made up of simple mols. This conclusion is confirmed by the behavior of H2O when it crystallizes spontaneously, and by the influence of pressure upon this process; it behaves, namely, as if it were a two-component system, the influence of pressure in the one case being exactly equivalent to the influence of conc. in the other. Further, the facts that ice II and III are stable within the same regions, and that the curves defining the equilibrium of either with ice I lie very close together, indicate that the mol. structure of ice II and III are the same, while that of ice I is different. Ice IV, which is lighter and less stable than ice 1, is formed when H2O crystallizes spontaneously under pressure; it could not be obtained at ordinary pressure, as it appears to be transformed into ice I at temps. somewhat below 0°. A point of some interest mentioned by the author is that water in freezing cannot exert a pressure in excess Of 2500 atm., since at that point ice III is stable and its formation is not accompanied by an expansion. From this it is evident that a vessel capable of withstanding a pressure of 2500 atm. will not be burst by the freezing of H2O.
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Tammann, G. Ice III. Z. Anorg. Chem. 1909, 63, 285– 305, DOI: 10.1002/zaac.19090630122
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Bridgman, P. W. Verhalten des Wassers als Flüssigkeit und in fünf festen Formen unter Druck. Anorg. Chem. 1912, 77, 377– 455, DOI: 10.1002/zaac.19120770130
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Engelhardt, H.; Whalley, E. Ice IV. J. Chem. Phys. 1972, 56, 2678– 2684, DOI: 10.1063/1.1677596
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Ice IV
Engelhardt, H.; Whalley, E.
Journal of Chemical Physics (1972), 56 (6), 2678-84CODEN: JCPSA6; ISSN:0021-9606.
Samples of ice IV were made and recovered in a metastable state at liq.-N temp. by using the nucleators discovered by Evans and a modification of his technique. No appreciable thermal effect that can be assocd. with a phase transition was obsd. on cooling. During the course of the prepn., measurements were made of the melting lines of ice III, IV, V, and VI. The intersections of these lines allows the coordinates of the hitherto unreported triple points III-IV-L and III-VI-L for both H2O and D2O and IV-VI-L for H2O to be obtained as well as new values of the coordinates of known triple points. The equil. pressure pe of a 1st-order phase transformation is given by pe = -ΔA/ΔV where ΔA and ΔV are the changes of the Helmholtz energy and the vol. at the transition. By using this equation, the effect of isotopic substitution on solid-solid transitions is shown to be caused by the change of vibration frequencies at a transition and for the phases of ice is largely caused by the change of the zero-point energy of the vibrations.
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Bridgman, P. W. The Pressure-Volume-Temperature Relations of the Liquid, and the Phase Diagram of Heavy Water. J. Chem. Phys. 1935, 3, 597– 605, DOI: 10.1063/1.1749561
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The pressure-volume-temperature relations of the liquid, and the phase diagram of heavy water
Bridgman, P. W.
Journal of Chemical Physics (1935), 3 (), 597-605CODEN: JCPSA6; ISSN:0021-9606.
The p-v-t relations of both liquid D2O and H2O were detd. by the sylphon method (C. A. 25, 2889; 27, 3127) from -20° to 95° and up to 12,000 kg./sq. cm., and the transition parameters in the range -60° to +20° and up to about 9000 kg./sq. cm. An unstable modification of solid D2O, designated IV, was found in the field of stability of phase V. The corresponding modification of H2O also exists (C. A. 6, 1084). In general the properties of H2O and of D2O covered by these measurements are very much alike, and differ in the direction suggested by the greater zero-point energy of H2O: the molar vol. of D2O is always greater than that of H2O at the same pressure and temp., and the transition lines of D2O always run at higher temps. In finer detail, however, the differences between the two waters do not vary regularly, and probably other considerations than of zero-point energy alone are necessary for a complete explanation.
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Kagi, H.; Lu, R.; Davidson, P.; Goncharov, A. F.; Mao, H. K.; Hemley, R. J. Evidence for Ice VI as an Inclusion in Cuboid Diamonds from High P-T Near Infrared Spectroscopy. Mineral. Mag. 2000, 64, 1089– 1097, DOI: 10.1180/002646100549904
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Tschauner, O.; Huang, S.; Greenberg, E.; Prakapenka, V. B.; Ma, C.; Rossman, G. R.; Shen, A. H.; Zhang, D.; Newville, M.; Lanzirotti, A. Ice-VII Inclusions in Diamonds: Evidence for Aqueous Fluid in Earth’s Deep Mantle. Science 2018, 359, 1136– 1139, DOI: 10.1126/science.aao3030
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Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth's deep mantle
Tschauner, O.; Huang, S.; Greenberg, E.; Prakapenka, V. B.; Ma, C.; Rossman, G. R.; Shen, A. H.; Zhang, D.; Newville, M.; Lanzirotti, A.; Tait, K.
Science (Washington, DC, United States) (2018), 359 (6380), 1136-1139CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
Water-rich regions in Earth's deeper mantle are suspected to play a key role in the global water budget and the mobility of heat-generating elements. We show that ice-VII occurs as inclusions in natural diamond and serves as an indicator for such water-rich regions. Ice-VII, the residue of aq. fluid present during growth of diamond, crystallizes upon ascent of the host diamonds but remains at pressures as high as 24 gigapascals; it is now recognized as a mineral by the International Mineralogical Assocn. In particular, ice-VII in diamonds points toward fluid-rich locations in the upper transition zone and around the 660-km boundary.
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Smit, K. V.; Shirey, S. B. Diamonds Help Solve the Enigma of Earth’s Deep Water. Gems Gemol. 2018, 54, 220– 223
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Consolmagno, G. J. Ice-Rich Moons and the Physical Properties of Ice. J. Phys. Chem. A 1983, 87, 4204– 4208, DOI: 10.1021/j100244a045
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Warren, S. G. Optical Constants of Ice from the Ultraviolet to the Microwave. Appl. Opt. 1984, 23, 1206– 1225, DOI: 10.1364/AO.23.001206
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Optical constants of ice from the ultraviolet to the microwave
Warren, Stephen G.
Applied Optics (1984), 23 (8), 1206-25CODEN: APOPAI; ISSN:0003-6935.
A review with 59 refs. A compilation of the optical consts. of ice Ih is made for temps. within 60 K of the m.p. The imaginary part mim of the complex index of refraction m was obtained from measurements of spectral absorption coeff.; the real part mre was computed to be consistent with mim by use of known dispersion relations. The compilation of mim requires subjective interpolation in the near-UV and microwave, a temp. correction in the far-IR, and a choice between 2 conflicting sources in the near-IR. New measurements of the spectral absorption coeff. of pure ice are needed, at temps. near the m.p., for 185-400-nm, 1.4-2.8-μm, 3.5-4.3 μm, 33-600-μm, and 1-100-mm wavelengths.
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Warren, S. G.; Brandt, R. E. Optical Constants of Ice from the Ultraviolet to the Microwave: A Revised Compilation. J. Geophys. Res. 2008, 113, D14220 DOI: 10.1029/2007JD009744
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Bertie, J. E.; Whalley, E. Infrared Spectra of Ices II, III, and V in the Range 4000 to 350 cm^–1. J. Chem. Phys. 1964, 40, 1646– 1659, DOI: 10.1063/1.1725374
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Infrared spectra of ices II, III, and V in the range 4000 to 350 cm.-1
Bertie, J. E.; Whalley, E.
Journal of Chemical Physics (1964), 40 (6), 1646-59CODEN: JCPSA6; ISSN:0021-9606.
The infrared spectra of ices II, III, and V between 4000 and 350 cm.-1 have been obtained. The ices were made at appropriate pressures and temperatures, cooled under pressure to liquid-nitrogen temperature, and removed from the pressure vessel. Mulls were made near liquid-nitrogen temperature by using isopentane or perfluoropropane as mulling agents, and the spectra of the mulls at ∼100°K. were recorded. The spectra of ices made from H2O, D2O, 5% H2O in D2O, 5% D2O in H2O, and, for ices II and III, 1% D2O in H2O were obtained. In general features, the spectra of pure H2O and D2O ices II, III, and V are similar to those of ice I. For most bands there is a shift of frequency from that in ice I towards the vapor frequencies, but the shift is small compared with the shift between ice I and the vapor. Ices II, III, and V are, therefore, essentially fully hydrogen bonded and are probably four coordinated. This agrees with a proposed structure for ice III. In ices II and III the bands due to the O-H and the O-D stretching vibrations of HDO in dilute solution in D2O and H2O, respectively, show a good deal of fine structure, and are quite narrow, the half-width of the O-D bands being about 5 cm.-1 These are by far the sharpest O-H (or O-D) stretching vibrations of hydrogen-bonded O-H-O groups so far observed. Clearly, breadth is not inherent in the O-H stretching bands of O-H-O. There is also a good deal of fine structure in the bands due to rotational vibrations of water molecules in ices II and III, and much of this fine structure broadens and weakens when a small amount of H2O is added to D2O, and of D2O to H2O. The only simple explanation of this, and of the fine structure of the O-H stretching bands, is that the hydrogen atoms in ices II and III are ordered. No corresponding fine structure occurs in ice V, and the hydrogen atoms are probably disordered, as in ice I.
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Engelhardt, H.; Whalley, E. The Infrared Spectrum of Ice IV in the Range 4000-400 cm^–1. J. Chem. Phys. 1979, 71, 4050– 4051, DOI: 10.1063/1.438173
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The infrared spectrum of ice IV in the range 4000-400 cm-1
Engelhardt, H.; Whalley, E.
Journal of Chemical Physics (1979), 71 (10), 4050-1CODEN: JCPSA6; ISSN:0021-9606.
The IR spectrum of ice IV was recorded in the range 400-4000 cm-1. The location and breadth of the bands confirm that the H2O mols. in ice IV are moderately strongly hydrogen bonded, as they are in the other phases of ice, and are orientationally disordered.
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Bertie, J. E.; Labbe, H. J.; Whalley, E. Infrared Spectrum of Ice VI in the Range 4000 - 50 cm^-1. J. Chem. Phys. 1968, 49, 2141– 2144, DOI: 10.1063/1.1670377
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Infrared spectrum of ice VI in the range 4000-50 cm.-1
Bertie, J. E.; Labbe, H. J.; Whalley, E.
Journal of Chemical Physics (1968), 49 (5), 2141-4CODEN: JCPSA6; ISSN:0021-9606.
The ir spectrum of ice VI recovered at liq.-N temp. and atm. pressure has been investigated in the range 4000-50 cm.-1 The spectrum closely resembles that of ice V, and shows conclusively that ice VI is orientationally disordered when recovered in this way.
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Bertie, J. E.; Labbe, H. J.; Whalley, E. Far-Infrared Spectra of Ice II, V and IX. J. Chem. Phys. 1968, 49, 775– 780, DOI: 10.1063/1.1670138
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Far-infrared spectra of ice II, V, and IX
Bertie, J. E.; Labbe, H. J.; Whalley, E.
Journal of Chemical Physics (1968), 49 (2), 775-80CODEN: JCPSA6; ISSN:0021-9606.
The far-ir spectra of ice II, V, and IX as recovered at liq.-N temp. and atm. pressure have been obtained in the range 360-20 cm.-1 to complement an earlier investigation in the range 4000-350 cm.-1 The bands of ice II and IX are sharp, as is characteristic of ordered crystals, whereas those of ice V are broad, as is characteristic of orientationally disordered crystals. These observations agree with previous conclusions about these phases.
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Minčeva-Śukarova, B.; Sherman, W. F.; Wilkinson, G. R. A High-Pressure Spectroscopic Study of the Ice III - Ice IX, Disordered - Ordered Transition. J. Mol. Struct. 1984, 115, 137– 140, DOI: 10.1016/0022-2860(84)80033-2
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A high pressure spectroscopic study on the ice III-ice IX, disordered-ordered transition
Minceva-Sukarova, B.; Sherman, W. F.; Wilkinson, G. R.
Journal of Molecular Structure (1984), 115 (), 137-40CODEN: JMOSB4; ISSN:0022-2860.
The only published data on the disordered-to-ordered ice III to ice IX transition refers to measurements of dielec. const. Raman spectra of ice III and ice IX were recorded under a pressure of 0.3 GPa for temps. of 130-250 K. They clearly show a transition that is predominantly of the disordered-ordered type. Raman spectra in the frequency range 15-4000 cm-1 are shown, but special attention is given to 2 translational lattice modes at ∼190 cm-1 and 65.5 cm-1 which show somewhat unusual behavior. Small discontinuities in the frequency vs. temp. plots suggest that there is a small discontinuous decrease in the vol. during the ice III to the ice IX transition.
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Minčeva-Śukarova, B.; Sherman, W. F.; Wilkinson, G. R. The Raman Spectra of Ice (I_h, II, III, V, VI and IX) as Functions of Pressure and Temperature. J. Phys. C: Solid State Phys. 1984, 17, 5833– 5850, DOI: 10.1088/0022-3719/17/32/017
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The Raman spectra of ice (Ih, II, III, V, VI and IX) as functions of pressure and temperature
Minceva-Sukarova, B.; Sherman, W. F.; Wilkinson, G. R.
Journal of Physics C: Solid State Physics (1984), 17 (32), 5833-50CODEN: JPSOAW; ISSN:0022-3719.
The Raman spectra of various forms of ice Ih, II, III, IX, V and VI of H2O, D2O, H218O and small percentages of HOD in both D2O and H2O were recorded in their true regions of stability. The high-pressure low-temp. Raman cell used for this work is described. The influence of pressure on the OH and OD stretching modes and the lattice vibrational frequencies is discussed. It is estd. that the pressure compresses the O-O bond lengths on av. about 5 pm-GPa-1 in the Ih, II, III and V types of ice. An attempt was made to correlate the available spectroscopic and crystallog. data for the various forms of ice to make assignments of the Raman- and IR-active lattice vibrational spectra.
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Salzmann, C. G.; Kohl, I.; Loerting, T.; Mayer, E.; Hallbrucker, A. Raman Spectroscopic Study on Hydrogen Bonding in Recovered Ice IV. J. Phys. Chem. B 2003, 107, 2802– 2807, DOI: 10.1021/jp021534k
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20
Raman Spectroscopic Study on Hydrogen Bonding in Recovered Ice IV
Salzmann, Christoph G.; Kohl, Ingrid; Loerting, Thomas; Mayer, Erwin; Hallbrucker, Andreas
Journal of Physical Chemistry B (2003), 107 (12), 2802-2807CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
Ice IV was prepd. in a reproducible manner on heating high-d. amorphous ice (HDA) at pressure of 0.81 GPa up to ≈162 K at a slow rate of ≈0.5 K min-1, quenching thereafter to 77 K, and recovering the sample under liq. N2 at 1 bar. Recovered ice IV was characterized by x-ray diffraction and it was free of HDA or of low-d. amorphous ice. D2O ice IV contained no cryst. impurities, whereas the HO sample contained a minor impurity of ice XII. D2O ice IV with 11 mol % HOD and HO ice IV with 9.0 mol % HOD were studied in vacuo by Raman spectroscopy between 80 and 145 K. The decoupled O-D (O-H) stretching band in H2O (D2O) ice IV consists of two overlapping peaks centered at 2500(3390) and 2458(3322) cm-1 at 80 K. Peak max. of the coupled O-H (O-D) stretching band region is at 3200(2360) cm-1. At low frequency a band at ≈498 (≈365) cm-1 is assigned to a librational mode, whereas bands at ≈252 (≈250), 208(203), 178(172), 152(149) and 126(123) cm-1 originate from translation modes. On heating ice IV, the authors measured the development of peak-positions and the phase transition from ice IV to ice I. The authors did not observe indication for formation of an amorphous phase during this transition. Curve resoln. of the decoupled O-D stretching transition region into two component bands is consistent with the assignment of the high-frequency band centered at 2500 cm-1 to the O-D···O H-bonds with 2.88 and 2.92 Å length, and of the low-frequency component band centered at 2458 cm-1 to H-bonds with 2.79 and 2.81 Å length. The composite band shape is consistent with large fwhh's (full width at half-heights) of the distinct bands from the four types of H-bonds.
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Salzmann, C.; Kohl, I.; Loerting, T.; Mayer, E.; Hallbrucker, A. The Raman Spectrum of Ice XII and Its Relation to That of a New “High-Pressure Phase of H₂O Ice”. J. Phys. Chem. B 2002, 106, 1– 6, DOI: 10.1021/jp012755d
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The Raman Spectrum of Ice XII and Its Relation to that of a New "High-Pressure Phase of H2O Ice"
Salzmann, Christoph; Kohl, Ingrid; Loerting, Thomas; Mayer, Erwin; Hallbrucker, Andreas
Journal of Physical Chemistry B (2002), 106 (1), 1-6CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
By comparison of Raman spectra probably the new high-pressure phase of H2O ice reported by Chou et al. (Science 1998, 281, 809) is in fact ice XII. Pure ice XII was prepd. in a reproducible manner on heating high-d. amorphous ice (HDA) at a pressure of 0.81 GPa up to ≈180 K at a rate of 25 K min-1, quenching thereafter to 77 K, and recovering the sample under liq. N2 at 1 bar. Recovered ice XII was characterized by x-ray diffraction and it was free of HDA, of low-d. amorphous ice, and of ice IV. H2O ice XII contg. 11 mol % HOD and D2O ice XII with 9.0 mol % HDO were studied by Raman spectroscopy between 80 and 150 K. The decoupled O-D (O-H) stretching band in H2O (D2O) ice XII consists of a nearly sym. band, slightly skewed at low frequency, which is centered at 80 K at 2473 (≈3340) cm-1, with full-width at half-height (fwhh) of 44 (≈80) cm-1. At low frequency a broad band at ≈470 (≈360) cm-1 and a sharp band at 195(190) cm-1 are assigned to the librational and translational mode in H2O (D2O) ice XII. The main feature of the decoupled O-D stretching band is attributed to the H bonds with O-D-O distance of 2.803 Å and multiplicity 6 obtained from neutron diffraction. The 2nd O-D-O distance of 2.766 Å with multiplicity 2 is expected to give a decoupled O-D component peak sepd. only ≈28 cm-1 from the main peak. These two component bands would appear as distinct peaks only when their fwhh is small, that is when ice XII is proton ordered. However, the composite band shape is consistent with large fwhh and proton disorder in ice XII. The authors did not observe indication for formation of an amorphous phase as intermediate on the ice XII → cubic ice phase transition, which is consistent with the authors' previous x-ray diffraction study. However, the results are in conflict with a recent report of the Raman spectrum of ice XII and of formation of amorphous ice on careful annealing of ice XII by Tulk and Klug (Phys. Rev. B 2001, 63, 212201-1).
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Salzmann, C. G.; Hallbrucker, A.; Finney, J. L.; Mayer, E. Raman Spectroscopic Features of Hydrogen-Ordering in Ice XII. Chem. Phys. Lett. 2006, 429, 469– 473, DOI: 10.1016/j.cplett.2006.08.079
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Raman spectroscopic features of hydrogen-ordering in ice XII
Salzmann, Christoph G.; Hallbrucker, Andreas; Finney, John L.; Mayer, Erwin
Chemical Physics Letters (2006), 429 (4-6), 469-473CODEN: CHPLBC; ISSN:0009-2614. (Elsevier B.V.)
The Raman spectra of recovered H ordered H2O and D2O ice XIV were recorded and compared with the spectra of the corresponding H disordered phase (ice XII). On heating ice XIV, the transition to ice XII is obsd. Subsequent cooling leads to the weak reappearance of ice XIV lattice vibrational peaks which demonstrates the reversibility of the H order ↹ disorder phase transition. However, cooling at ambient pressure produces a less ordered ice XIV than cooling under pressure which implies that pressure favors H ordering of ice XII.
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Salzmann, C. G.; Hallbrucker, A.; Finney, J. L.; Mayer, E. Raman Spectroscopic Study of Hydrogen Ordered Ice XIII and of Its Reversible Phase Transition to Disordered Ice V. Phys. Chem. Chem. Phys. 2006, 8, 3088– 3093, DOI: 10.1039/b604360g
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Raman spectroscopic study of hydrogen ordered ice XIII and of its reversible phase transition to disordered ice V
Salzmann, Christoph G.; Hallbrucker, Andreas; Finney, John L.; Mayer, Erwin
Physical Chemistry Chemical Physics (2006), 8 (26), 3088-3093CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
Raman spectra of recovered ordered H2O (D2O) ice XIII doped with 0.01 M HCl (DCl) recorded in vacuo at 80 K are reported in the range 3600-200 cm-1. The bands are assigned to the various types of modes from isotope ratios. On thermal cycling between 80 and 120 K, the reversible phase transition to disordered ice V is obsd. The remarkable effect of HCl (DCl) on orientational ordering in ice V and its phase transition to ordered ice XIII, 1st reported in a powder neutron diffraction study of DCl doped D2O ice V (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758), is demonstrated by Raman spectroscopy and discussed. The dopants KOH and HF have only a minor effect on H ordering in ice V, as shown by the Raman spectra.
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Whale, T. F.; Clark, S. J.; Finney, J. L.; Salzmann, C. G. DFT-Assisted Interpretation of the Raman Spectra of Hydrogen-Ordered Ice XV. J. Raman Spectrosc. 2013, 44, 290– 298, DOI: 10.1002/jrs.4170
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DFT-assisted interpretation of the Raman spectra of hydrogen-ordered ice XV
Whale, Thomas F.; Clark, Stewart J.; Finney, John L.; Salzmann, Christoph G.
Journal of Raman Spectroscopy (2013), 44 (2), 290-298CODEN: JRSPAF; ISSN:0377-0486. (John Wiley & Sons Ltd.)
The vibrational spectra of the condensed phases of water often show broad and strongly overlapping spectral features which can make spectroscopic interpretations and peak assignments difficult. The Raman spectra of hydrogen-ordered H2O and D2O ice XV are reported here, and it is shown that the spectra can be fully interpreted in terms of assigning normal modes to the various spectral features by using d. functional theory (DFT) calcns. The calcd. lattice-vibration spectrum of the exptl. antiferroelec. P1 structure is in good agreement with the exptl. data whereas the spectrum of a ferroelec. Cc structure, which computational studies have suggested as the crystal structure of ice XV, differs substantially. Moreover, the calcd. P1 coupled O-H stretch spectrum also seems in better agreement with the expt. than the calcd. spectrum for the Cc structure. Both the hydrogen bonds as well as the covalent bonds appear to be stronger in hydrogen-ordered ice XV than in the hydrogen-disordered counterpart ice VI. A new type of stretching mode is identified, and it is speculated that this kind of mode might be relevant for other condensed water phases as well. Furthermore, the ice XV spectra are compared to the spectra of ice VIII which is the only other high-pressure phase of ice for which detailed spectroscopic assignments have been made so far. In summary, we have established a link between crystallog. data and spectroscopic information in the case of ice XV by using DFT-calcd. spectra. Such correlations may eventually help interpreting the vibrational spectra of more structurally-disordered aq. systems.
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Thoeny, A. V.; Gasser, T. M.; Loerting, T. Distinguishing Ice β-XV from Deep Glassy Ice VI: Raman Spectroscopy. Phys. Chem. Chem. Phys. 2019, 21, 15452– 15462, DOI: 10.1039/C9CP02147G
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Distinguishing ice β-XV from deep glassy ice VI: Raman spectroscopy
Thoeny, Alexander V.; Gasser, Tobias M.; Loerting, Thomas
Physical Chemistry Chemical Physics (2019), 21 (28), 15452-15462CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
The nature of the hydrogen sublattice of an HCl-doped ice VI sample after cooling at 1.8 GPa has been a topic of recent interest. The samples are interpreted either as the new H-ordered ice phase ice β-XV with a thermodn. stability region in the phase diagram [T. M. Gasser et al., Chem. Sci., 2018, 9, 4224], or alternatively as H-disordered, deep glassy ice VI [A. Rosu-Finsen and C. G. Salzmann, Chem. Sci., 2019, 10, 515]. Here we provide a comprehensive Raman spectroscopic study on ice β-XV, ice XV and ice VI, with the following key findings: (i) the Raman spectra of ice β-XV differ fundamentally from those of ice VI and ice XV, where the degree of H-order is even higher than in ice XV. (ii) Upon cooling ice VI there is competition between formation of ice XV and ice β-XV domains, where ice XV forms at 0.0 GPa, but ice β-XV at 1.8 GPa. Domains of ice β-XV are present in literature "ice XV" at 1.0 GPa. This result clarifies the puzzling earlier observation that the degree of H-order in ice XV apparently improves upon heating and recooling at ambient pressure. In reality, this procedure leaves the H-order in ice XV unaffected, but removes ice β-XV domains by transforming them to ice XV. (iii) Upon heating, the samples experience the transition sequence ice β-XV → ice XV → ice VI, i.e., an order-order transition at 103 K followed by an order-disorder transition at 129 K. The former progresses via a disordered transient state. (iv) D2O ice β-XV forms upon cooling DCl-doped D2O-ice VI, albeit at a much lower pace than in the hydrogenated case so that untransformed D2O ice VI domains are present even after slow cooling. The librational band at 380 cm-1 is identified to be the characteristic spectroscopic feature of deuterated ice β-XV. Taken together these findings clarify open questions in previous work on H-ordering in the ice VI lattice, rule out a glassy nature of ice β-XV and pave the way for a future neutron diffraction study to refine the crystal structure of D2O ice β-XV.
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Clark, R. N. Water Frost and Ice - the Near Infrared Spectral Reflectance at 0.65–2.5 μm. J. Geophys. Res. 1981, 86, 3087– 3096, DOI: 10.1029/JB086iB04p03087
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Water frost and ice: the near-infrared spectral reflectance 0.65-2.5 μm
Clark, Roger N.
Journal of Geophysical Research, B (1981), 86 (B4), 3087-96CODEN: JJGBDU; ISSN:0196-6936.
The spectral reflectance of H2O frost and frost on ice as a function of temp. and grain size is presented with 11/2% spectral resoln. in the 0.65- to 2.5-μm wavelength region. The well-known 2.0-, 1.65-, and 1.5-μm solid H2O absorption bands are precisely defined along with the little studied 1.25-μm band and the previously unidentified (in reflectance) 1.04-, 0.90-, and 0.81-μm absorption bands. The 1.5-μm band complex is quant. analyzed using a nonlinear least squares algorithm to resolve the band into 4 Gaussian components as a function of grain size and temp. The 1.65-μm component, which was thought to be a good temp. sensor, is highly grain size dependent and poorly suited to temp. sensing. Another Gaussian component appears to show a dependence of width on grain size while being independent of temp. The relative apparent band depths are different for frost layers on ice than for thick layers of frost and may explain the apparent band depths seen in many planetary reflectance spectra.
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Grundy, W. M.; Schmitt, B. The Temperature-Dependent Near-Infrared Absorption Spectrum of Hexagonal H₂O Ice. J. Geophys. Res. 1998, 103, 25809– 25822, DOI: 10.1029/98JE00738
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The temperature-dependent near-infrared absorption spectrum of hexagonal H2O ice
Grundy, W. M.; Schmitt, B.
Journal of Geophysical Research, [Planets] (1998), 103 (E11), 25809-25822CODEN: JGPLEH; ISSN:1934-8592. (American Geophysical Union)
Transmission spectra were measured between 1.0 and 2.7 μm for monocryst. samples of hexagonal water ice at temps. between 20 and 270 K. Samples were crystd. from liq. water within closed cells, with thicknesses ranging from 100 μm to 1.0 cm. The absorption spectrum of ice changes with temp. in several ways. With higher temp., the shapes of absorption bands become more smoothed, the strengths of some absorption bands decrease, the absorption in continuum wavelengths increases, and the band centers of some absorption bands shift to shorter wavelengths. In this paper we present the new absorption coeff. spectra along with an examn. of the different temp. effects. These data should prove extremely valuable for anal. of near-IR reflectance spectra of low-temp. icy surfaces, such as those of outer solar system satellites, Kuiper Belt objects, Pluto and Charon, comet nuclei, the polar caps of Mars, and terrestrial snow- and ice-covered regions. The data may also be of value in simulating radiative transfer in clouds of ice particles in the atmospheres of planets.
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Leto, G.; Gomis, O.; Strazzulla, G. The Reflectance Spectrum of Water Ice: Is the 1.65 μm Peak a Good Temperature Probe?. Mem. Soc. Astron. Ital. Suppl. 2005, 6, 57– 62
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Tonauer, C. M.; Seidl-Nigsch, M.; Loerting, T. High-Density Amorphous Ice: Nucleation of Nanosized Low-Density Amorphous Ice. J. Phys.: Condens. Matter 2018, 30, 034002 DOI: 10.1088/1361-648X/aa9e76
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High-density amorphous ice: nucleation of nanosized low-density amorphous ice
Tonauer, Christina M.; Seidl-Nigsch, Markus; Loerting, Thomas
Journal of Physics: Condensed Matter (2018), 30 (3), 034002/1-034002/11CODEN: JCOMEL; ISSN:0953-8984. (IOP Publishing Ltd.)
The pressure dependence of the crystn. temp. of different forms of expanded high-d. amorphous ice (eHDA) was scrutinized. Crystn. at pressures 0.05- 0.30 GPa was followed using volumetry and powder x-ray diffraction. eHDA samples were prepd. via isothermal decompression of very high-d. amorphous ice at 140 K to different end pressures between 0.07-0.30 GPa (eHDA0.07-0.3). At 0.05-0.17 GPa the crystn. line Tx (p) of all eHDA variants is the same. At pressures >0.17 GPa, all eHDA samples decompressed to pressures <0.20 GPa exhibit significantly lower Tx values than eHDA0.2 and eHDA0.3. We rationalize our findings with the presence of nanoscaled low-d. amorphous ice (LDA) seeds that nucleate in eHDA when it is decompressed to pressures <0.20 GPa at 140 K. Below ∼0.17 GPa, these nanosized LDA domains are latent within the HDA matrix, exhibiting no effect on Tx of eHDA<0.2. Upon heating at pressures ≥0.17 GPa, these nanosized LDA nuclei transform to ice IX nuclei. They are favored sites for crystn. and, hence, lower Tx. By comparing crystn. expts. of bulk LDA with the ones involving nanosized LDA we are able to est. the Laplace pressure and radius of ∼0.3-0.8 nm for the nanodomains of LDA. The nucleation of LDA in eHDA revealed here is evidence for the first-order-like nature of the HDA → LDA transition, supporting water's liq.-liq. transition scenarios.
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Mishima, O.; Endo, S. Phase Relations of Ice under Pressure. J. Chem. Phys. 1980, 73, 2454– 2456, DOI: 10.1063/1.440396
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Phase relations of ice under pressure
Mishima, O.; Endo, S.
Journal of Chemical Physics (1980), 73 (5), 2454-6CODEN: JCPSA6; ISSN:0021-9606.
The transitions between various ice polymorphs were obsd. with a manganin sensor under pressure. The stable region of ice V disappeared at low temp. and the direct transition from ice II to ice VI was obsd. The triple point of ice II, V, and VI exists in the neighborhood of -60° and 6 kbar. The P-T phase diagram of H2O was constructed.
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Shephard, J. J.; Salzmann, C. G. The Complex Kinetics of the Ice VI to Ice XV Hydrogen Ordering Phase Transition. Chem. Phys. Lett. 2015, 637, 63– 66, DOI: 10.1016/j.cplett.2015.07.064
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The complex kinetics of the ice VI to ice XV hydrogen ordering phase transition
Shephard, Jacob J.; Salzmann, Christoph G.
Chemical Physics Letters (2015), 637 (), 63-66CODEN: CHPLBC; ISSN:0009-2614. (Elsevier B.V.)
The reversible phase transition from hydrochloric-acid-doped ice VI to its hydrogen-ordered counterpart ice XV is followed using differential scanning calorimetry. Upon cooling at ambient pressure fast hydrogen ordering is obsd. at first followed by a slower process which manifests as a tail to the initial sharp exotherm. The residual hydrogen disorder in H2O and D2O ice XV is detd. as a function of the cooling rate. We conclude that it will be difficult to obtain fully hydrogen-ordered ice XV by cooling at ambient pressure. Our new exptl. findings are discussed in the context of recent computational work on ice XV.
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Mishima, O.; Calvert, L. D.; Whalley, E. ″Melting Ice″ I at 77 K and 10 kbar: A New Method of Making Amorphous Solids. Nature 1984, 310, 393– 395, DOI: 10.1038/310393a0
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'Melting ice' I at 77 K and 10 kbar: a new method of making amorphous solids
Mishima, O.; Calvert, L. D.; Whalley, E.
Nature (London, United Kingdom) (1984), 310 (5976), 393-5CODEN: NATUAS; ISSN:0028-0836.
A new way is reported of prepg. an amorphous solid, by melting a solid by pressure below the glass transition of the liq., and it is applied to making a new kind of amorphous ice. Thus, ice I was transformed to an amorphous phase, as detd. by x-ray diffraction, by pressurizing it at 77 K to its extrapolated m.p. of 10 kbar. At the m.p., the fluid is well below its glass transition. On heating at a rate of ∼2.6 K min-1 at zero pressure it transforms at ∼117 K to a 2nd amorphous phase with a heat evolution of 42 ± ∼8 J g-1, and at ∼152 K further transforms to ice I with a heat evolution of 92 ± ∼15 J g-1. In 1 sample, ice Ic was formed and in another, existing crystals of ice Ih grew from the amorphous phase. Heating below the 117 K transition causes irreversible changes in the diffraction pattern, and a continuous range of amorphous phases can be made. Similar transformations will probably occur in all solids whose m.p. decreases with increasing pressure if they can be cooled sufficiently for a transformation to a cryst. solid to be too slow.
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Petrenko, V. F.; Whitworth, R. W. Physics of Ice; Oxford University Press: Oxford, 1999.
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Bertie, J. E.; Whalley, E. Infrared Spectra by Mulling Techniques at Liquid Nitrogen Temperatures. Spectrochim. Acta 1964, 20, 1349– 1356, DOI: 10.1016/0371-1951(64)80115-6
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Infrared spectra by mulling techniques at liquid-nitrogen temperatures
Bertie, J. E.; Whalley, E.
Spectrochimica Acta (1964), 20 (9), 1349-56CODEN: SPACA5; ISSN:0038-6987.
An exptl. technique is described for making spectroscopic mulls near liquid-N temps. This technique allows such materials to be examd. spectroscopically and the phase to be verified relatively easily by x-ray diffraction. The most useful mulling agents are propane, propylene, and chlorotrifluoromethane. Perfluoropropane and isopentane are possible mulling agents, but are not as useful as those mentioned above because their m.ps. are rather high.
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Bertie, J. E.; Whalley, E. Infrared Spectra of Ices I_h and I_c in the Range 4000 to 350 cm^–1. J. Chem. Phys. 1964, 40, 1637– 1645, DOI: 10.1063/1.1725373
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Infrared spectra of ices Ih and Ic in the range 4000 to 350 cm.-1
Bertie, J. E.; Whalley, E.
Journal of Chemical Physics (1964), 40 (6), 1637-45CODEN: JCPSA6; ISSN:0021-9606.
The infrared spectra of ice Ih made from H2O, D2O, a mixt. of 95% H2O and 5% D2O, and a mixt. of 5% H2O and 95% D2O, and of ice Ic made from H2O, D2O, and a mixt. of 95% H2O and 5% D2O, were recorded in the region 4000 to 350 cm.-1 by using low-temp. mulling techniques. The ice Ic was made by the transformation of ices II and III, and was authenticated by its x-ray diffraction powder pattern. The spectra of ices Ih and Ic are identical, within exptl. error. The spectra of ice Ih, while similar in their main features to those reported by earlier workers, differ significantly in detail, probably largely because much of the previous work, particularly on D2O ice, was done with partly vitreous ice. The usual interpretation of the bands in terms of the ν1, ν2, ν3, and νR vibrations of isolated mols. is greatly oversimplified because intermol. coupling is important. There are at least 6 (5 infrared and one Raman) bands due to O-D stretching vibrations in the spectrum of D2O ice I, but the detailed origin is unknown. The breadth of the O-H and O-D stretching bands of HDO in dil. soln. in D2O and H2O is interpreted as indicating a disarrangement of the O positions due to the disorder of the H atoms.
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Kubelka, P.; Munk, F. An Article on Optics of Paint Layers. Fuer Tekn. Phys. 1931, 12, 593– 609
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Torrent, J.; Barron, V. Diffuse Reflectance Spectroscopy; American Society of Agronomy and Soil Science: Madison, WI, 2015.
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Rajaram, B.; Glandorf, D. L.; Curtis, D. B.; Tolbert, M. A.; Toon, O. B.; Ockman, N. Temperature-Dependent Optical Constants of Water Ice in the near Infrared: New Results and Critical Review of the Available Measurements. Appl. Opt. 2001, 40, 4449– 4462, DOI: 10.1364/AO.40.004449
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Temperature-dependent optical constants of water ice in the near infrared: new results and critical review of the available measurements
Rajaram B; Glandorf D L; Curtis D B; Tolbert M A; Toon O B; Ockman N
Applied optics (2001), 40 (25), 4449-62 ISSN:1559-128X.
The optical constants of water ice have been determined in the near infrared from 4000 to 7000 cm(-1). Polycrystalline ice films with thickness as great as ~1164 mum were formed by condensation of water vapor on a cold silicon substrate at temperatures of 166, 176, 186, and 196 K. The transmission of light through the ice films was measured during their growth from 0 to 1164 mum over the frequency range of approximately 500-7000 cm(-1). The optical constants were extracted by means of simultaneously fitting the calculated transmission spectra of films of varying thickness to their respective measured transmission spectra with an iterative Kramers-Kronig technique. Equations are presented to account for reflection losses at the interfaces when the sample is held in a cell. These equations are used to reanalyze the transmission spectrum of water ice (358-mum sample at 247 K) recorded by Ockman in 1957 [Philos. Mag. Suppl. 7, 199 (1958)]. Our imaginary indices for water ice are compared with those of Gosse et al. [Appl. Opt. 34, 6582 (1995)], Kou et al. [Appl. Opt. 32, 3531 (1993)], Grundy and Schmitt [J. Geophys. Res. 103, 25809 (1998)], and Warren [Appl. Opt. 23, 1206 (1984)], and with the new indices from Ockman's spectrum. The temperature dependence in the imaginary index of refraction observed by us between 166 and 196 K and that between our data at 196 K and the data of Gosse et al. at 250 K are compared with that predicted by the model of Grundy and Schmitt. On the basis of this comparison a linear interpolation of the imaginary indices of refraction between 196 and 250 K is proposed. We believe that the accuracy of this interpolation is better than 20%.
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Ockman, N. The Infrared and Raman Spectra of Ice. Adv. Phys. 1958, 7, 199– 220, DOI: 10.1080/00018735800101227
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The infrared and Raman spectra of ice
Ockman, Nathan
(1958), 7 (), 199-220 ISSN:.
A review with bibliography.
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Ockman, N.; Sutherland, G. B. B. M. Infrared and Raman Spectra of Single Crystals of Ice. Proc. R. Soc. London 1958, 247, 434– 440, DOI: 10.1098/rspa.1958.0198
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Infrared and Raman spectra of single ice crystals
Ockman, N.; Sutherland, G. B. B. M.
Proceedings of the Royal Society of London, Series A: Mathematical, Physical and Engineering Sciences (1958), 247 (), 434-40CODEN: PRLAAZ; ISSN:1364-5021.
The infrared dichroism of single crystals of ice is not a very sensitive criterion for distinguishing among proposals about the location of H atoms in ice. The absence of dichroism in the fundamental frequencies eliminates 3 out of 7 proposed models. Only the Owston model (CA 48, 7383g) is completely excluded.
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Larsen, C. F.; Williams, Q. Overtone Spectra and Hydrogen Potential of H₂O at High Pressure. Phys. Rev. B 1998, 58, 8306– 8312, DOI: 10.1103/PhysRevB.58.8306
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Overtone spectra and hydrogen potential of H2O at high pressure
Larsen, Christopher F.; Williams, Quentin
Physical Review B: Condensed Matter and Materials Physics (1998), 58 (13), 8306-8312CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
The 1st overtones of the stretching and bending vibrations of H2O and the 1st stretching overtone of D2O pressures of 37 GPa at 300 K, encompassing the stability fields of H2O, ice VI, and ice VII. The successive disappearance of the overtone peaks in ice VII with increasing pressure indicates that the barrier height in the double min. H potential decreases at a rate of 230 cm-1 GPa-1 (0.029 eV GPa-1) to pressures of 32 GPa. The 1st overtone of the O-H stretching vibration splits and forms a doublet between 10 and 25 GPa, implying that the barrier height is near the energy of this overtone and that proton tunneling may occur at this energy level between 10 and 25 GPa. The frequency of the 1st stretching overtone of ice VII is also strongly influenced by quantum effects near the barrier top, as its frequency is larger than harmonic values. The H bonding potential in ice VII at high pressure is described using a semiempirical potential model that incorporates the obsd. rate of barrier height redn. and available O-H and O-O bond length data of ice VII under pressure. This model requires a rapid increase in O-H bond length between 40 and 60 GPa to reach a value of 1/2 the O-O distance >60 GPa, at which pressure the transition to ice X was reported to occur. Up to 40 GPa, the model is consistent with the trend of O-H bond length obsd. in neutron diffraction data to 10 GPa.
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Salzmann, C. G.; Radaelli, P. G.; Slater, B.; Finney, J. L. The Polymorphism of Ice: Five Unresolved Questions. Phys. Chem. Chem. Phys. 2011, 13, 18468– 18480, DOI: 10.1039/c1cp21712g
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The polymorphism of ice: five unresolved questions
Salzmann, Christoph G.; Radaelli, Paolo G.; Slater, Ben; Finney, John L.
Physical Chemistry Chemical Physics (2011), 13 (41), 18468-18480CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
A review. Our recent discovery of three new phases of ice has increased the total no. of known distinct polymorphs of ice to fifteen. In this Perspective article, we give a brief account of previous work in the field, and discuss some of the particularly interesting open questions that have emerged from recent studies. These include (i) the effectiveness of acid and base dopants to enable hydrogen-ordering processes in the ices, (ii) the comparison of the calorimetric data of some of the cryst. phases of ice and low-d. amorphous ice, (iii) the disagreement between the exptl. ice XV structure and computational predictions, (iv) the incompleteness of some of the hydrogen order/disorder pairs and (v) the new frontiers at the high and neg. pressure ends of the phase diagram.
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Grundy, W. M.; Buie, M. W.; Stansberry, J. A.; Spencer, J. R.; Schmitt, B. Near-Infrared Spectra of Icy Outer Solar System Surfaces: Remote Determination of H₂O Ice Temperatures. Icarus 1999, 142, 536– 549, DOI: 10.1006/icar.1999.6216
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Near-infrared spectra of icy outer Solar System surfaces: remote determination of H2O ice temperatures
Grundy, W. M.; Buie, M. W.; Stansberry, J. A.; Spencer, J. R.; Schmitt, B.
Icarus (1999), 142 (2), 536-549CODEN: ICRSA5; ISSN:0019-1035. (Academic Press)
We present new 1.20 to 2.35 μm spectra of satellites of Jupiter, Saturn, and Uranus, and the rings of Saturn, obtained in 1995 and 1998 at Lowell Observatory. For most of the target objects, our data provide considerable improvement in spectral resoln. and signal-to-noise over previously published data. Absorption bands with shapes characteristic of low-temp., hexagonal cryst. H2O ice dominate the spectra of most of our targets in this wavelength range. We make use of newly published temp.-dependent wavelengths and relative strengths of H2O absorption bands to infer ice temps. from our spectra. These ice temps. are distinct from temps. detd. from thermal emission measurements or simulations of radiative balances. Unlike those methods, which av. over all terrains including ice-free regions, our temp.-sensing method is only sensitive to the ice component. Our method offers a new constraint which, combined with other observations, can lead to better understanding of thermal properties and textures of remote, icy surfaces. Ice temps. are generally lower than thermal emission brightness temps., indicative of the effects of thermal inertia and segregation between ice and warmer, darker materials. We also present the results of expts. to investigate possible changes of water ice temp. over time, including observations of Titania at two epochs, and of Ganymede and saturnian ring particles following emergence from the eclipse shadows of their primary planets. Finally, we discuss limitations of our temp. measurement method which can result from the presence of H2O in phases other than hexagonal ice-Ih, such as amorphous ice, hydrated mineral phases, or radiation-damaged cryst. ice. Our spectra of Europa and Enceladus exhibit peculiar spectral features which may result from effects such as these. (c) 1999 Academic Press.
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44
Loerting, T.; Bauer, M.; Kohl, I.; Watschinger, K.; Winkel, K.; Mayer, E. Cryoflotation: Densities of Amorphous and Crystalline Ices. J. Phys. Chem. B 2011, 115, 14167– 14175, DOI: 10.1021/jp204752w
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44
Cryoflotation: Densities of Amorphous and Crystalline Ices
Loerting, Thomas; Bauer, Marion; Kohl, Ingrid; Watschinger, Katrin; Winkel, Katrin; Mayer, Erwin
Journal of Physical Chemistry B (2011), 115 (48), 14167-14175CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
The authors present an exptl. method aimed at measuring mass densities of solids at ambient pressure. The principle of the method is flotation in a mixt. of liq. N and liq. Ar, where the mixing ratio is varied until the solid hovers in the liq. mixt. The temp. of such mixts. is at 77-87 K, and therefore, the main advantage of the method is the possibility of detg. densities of solid samples, which are instable >90 K. The accessible d. range (∼0.81-1.40 g cm-3) is perfectly suitable for the study of cryst. ice polymorphs and amorphous ices. As a benchmark, the authors here det. densities of cryst. polymorphs (ices Ih, Ic, II, IV, V, VI, IX, and XII) by flotation and compare them with crystallog. densities. The reproducibility of the method is about ±0.005 g cm-3, and in general, the agreement with crystallog. densities is very good. Also, the authors show measurements on a range of amorphous ice samples and correlate the d. with the d spacing of the 1st broad halo peak in diffraction expts. Finally, the influence of microstructure, in particular voids, on the d. for the case of hyperquenched glassy H2O and cubic ice samples prepd. by deposition of micrometer-sized liq. droplets are discussed.
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45
Herrero, C. P.; Ramirez, R. Topological Characterization of Crystalline Ice Structures from Coordination Sequences. Phys. Chem. Chem. Phys. 2013, 15, 16676– 16685, DOI: 10.1039/c3cp52167b
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45
Topological characterization of crystalline ice structures from coordination sequences
Herrero, Carlos P.; Ramirez, Rafael
Physical Chemistry Chemical Physics (2013), 15 (39), 16676-16685CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
Topol. properties of cryst. ice structures are studied by considering ring statistics, coordination sequences, and topol. d. of different ice phases. The coordination sequences (no. of sites at topol. distance k from a ref. site) have been obtained by direct enumeration until at least 40 coordination spheres for different ice polymorphs. This allows us to study the asymptotic behavior of the mean no. of sites in the k-th shell, Mk, for high values of k: Mk ∼ ak2, a being a structure-dependent parameter. Small departures from a strict parabolic dependence have been studied by considering first and second differences of the series {Mk} for each structure. The parameter a ranges from 2.00 for ice VI to 4.27 for ice XII, and is used to define a topol. d. for these solid phases of water. Correlations between such topol. d. and the actual vol. of ice phases are discussed. Ices Ih and Ic are found to depart from the general trend in this correlation due to the large void space in their structures.
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Keishiro Yamashita, Thomas Loerting. Thermodynamically Stable Intermediate in the Course of Hydrogen Ordering from Ice V to Ice XIII. The Journal of Physical Chemistry Letters 2024, 15 (4) , 1181-1187. https://doi.org/10.1021/acs.jpclett.3c03411
Li Han, Haipeng Wang, Wensheng Cai, Xueguang Shao. Mechanism of Binding of Polyproline to Ice via Interfacial Water: An Experimental and Theoretical Study. The Journal of Physical Chemistry Letters 2023, 14 (18) , 4127-4133. https://doi.org/10.1021/acs.jpclett.3c00577
Aigerim Karina, Tobias Eklund, Christina M. Tonauer, Hailong Li, Thomas Loerting, Katrin Amann-Winkel. Infrared Spectroscopy on Equilibrated High-Density Amorphous Ice. The Journal of Physical Chemistry Letters 2022, 13 (34) , 7965-7971. https://doi.org/10.1021/acs.jpclett.2c02074
Christina M. Tonauer, Eva-Maria Köck, Raphael Henn, Josef N. Stern, Leonardo del Rosso, Milva Celli, Christoph Kappacher, Sophia Leiter, Christian G. Kirchler, Christian W. Huck, Thomas Loerting. Near-infrared Spectroscopy for Remote Sensing of Porosity, Density, and Cubicity of Crystalline and Amorphous H 2 O Ices in Astrophysical Environments. The Astrophysical Journal 2024, 970 (1) , 82. https://doi.org/10.3847/1538-4357/ad4f82
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Alberto Toffano, John Russo, Maria Rescigno, Umbertoluca Ranieri, Livia E. Bove, Fausto Martelli. Temperature- and pressure-dependence of the hydrogen bond network in plastic ice VII. The Journal of Chemical Physics 2022, 157 (9) https://doi.org/10.1063/5.0111189
Michal L. Chodkiewicz, Roman Gajda, Barbara Lavina, Sergey Tkachev, Vitali B. Prakapenka, Przemyslaw Dera, Krzysztof Wozniak. Accurate crystal structure of ice VI from X-ray diffraction with Hirshfeld atom refinement. IUCrJ 2022, 9 (5) , 573-579. https://doi.org/10.1107/S2052252522006662

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Published January 5, 2021

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Abstract
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Figure 1
Figure 1. NIR spectra measured at ∼77 K (in blue), together with MIR spectra recorded in the 1960s and 1970s by Whalley and co-workers at ∼100 K from refs (14−16,35) (in gray). NIR spectra are normalized with respect to the band at ∼5000 cm^–1. Band assignments are given, where “x” means “unassigned”. Please note in (c) that Bertie and Whalley called the sample “ice III” even though it was measured at ∼100 K, that is, below the ordering temperature to ice IX.
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Figure 2
Figure 2. Comparison of the NIR features at (a) 6600 cm^–1 and (b) 5000 cm ^–1. (c–f) Correlation plots: (c) mass density and peak position, (d) mass density and full width at one-third of the maximum (FWTM), (e) topological density and peak position, and (f) topological density and FWTM. Filled diamonds in (c) and (e) correspond to the ones shown in (a). Open symbols in (c) and (e) represent sub-bands as extracted using the procedure shown in Figure S4.
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References
This article references 45 other publications.
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  T. believes that the irregularities in the p-v and p-t curves for water between -20° and -80° and 1 kg. per sq. cm. and 12500 kg. per sq. cm. (data of Bridgman) are due to changes in the mol. species, which have different thermodynamic properties. The changes in species are the results of polymerization of the water.
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  Tammann, G. On the State Diagram of Water. Z. Phys. Chem. 1913, 84, 257– 292, DOI: 10.1515/zpch-1913-8418
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  The Diagram of State of Water
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  In this paper T. compares the recent data of Bridgman on the thermodynamic properties of water with his own, some of which he has redetd. for the occasion. Using this data, he works out anew the equil. curves between the various phases which are possible in the 1 component system between 0° and -60° and 2000 to 3000 kg per sq. cm.
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  Tammann, G. The Behaviour of Water at High Pressure and Low Temperatures. Z. Phys. Chem. 1910, 72, 609– 631, DOI: 10.1515/zpch-1910-7232
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  The Behavior of Water at High Pressures and Low Temperatures
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  Water at temps. below 0° exists in several forms which fall into two groups: (a) those which are lighter and (b) those which are heavier than liquid H2O. (a) ordinary hexagonal ice I, absolutely stable at pressures less than 2200, atm.; and the unstable forms: the tetragonal ice observed by Nordenskiold, the regular crystals described by Barendrecht, and ice IV discovered by the author; the last may be identical with one of the other two. (b) Ice III (cf. C. A., 4, 1415) and the less stable ice II. These can be realized at ordinary pressure below -130°. A triple point is exhibited by the system ice III - ice 1 - H2O at -22° and 2200 kg. per sq. cm.; by the system ice II - ice I - H2O at - 22.4° and 2230 kg. Diagrams are given which illustrate equilibrium conditions throughout the field. From the conditions under which the different forms are observed, the conclusion is reached that the varieties of group (a) form only from H2O rich in polymolecules, while ice II and III form only from H2O consisting mainly of simple mols. or by compressing ice I to such an extent that the polymolecules are no longer stable. On this view the forms belonging to group (a) are made up of associated mols., while those of group (b) are made up of simple mols. This conclusion is confirmed by the behavior of H2O when it crystallizes spontaneously, and by the influence of pressure upon this process; it behaves, namely, as if it were a two-component system, the influence of pressure in the one case being exactly equivalent to the influence of conc. in the other. Further, the facts that ice II and III are stable within the same regions, and that the curves defining the equilibrium of either with ice I lie very close together, indicate that the mol. structure of ice II and III are the same, while that of ice I is different. Ice IV, which is lighter and less stable than ice 1, is formed when H2O crystallizes spontaneously under pressure; it could not be obtained at ordinary pressure, as it appears to be transformed into ice I at temps. somewhat below 0°. A point of some interest mentioned by the author is that water in freezing cannot exert a pressure in excess Of 2500 atm., since at that point ice III is stable and its formation is not accompanied by an expansion. From this it is evident that a vessel capable of withstanding a pressure of 2500 atm. will not be burst by the freezing of H2O.
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  Tammann, G. Ice III. Z. Anorg. Chem. 1909, 63, 285– 305, DOI: 10.1002/zaac.19090630122
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  Bridgman, P. W. Verhalten des Wassers als Flüssigkeit und in fünf festen Formen unter Druck. Anorg. Chem. 1912, 77, 377– 455, DOI: 10.1002/zaac.19120770130
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  Engelhardt, H.; Whalley, E. Ice IV. J. Chem. Phys. 1972, 56, 2678– 2684, DOI: 10.1063/1.1677596
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  Ice IV
  Engelhardt, H.; Whalley, E.
  Journal of Chemical Physics (1972), 56 (6), 2678-84CODEN: JCPSA6; ISSN:0021-9606.
  Samples of ice IV were made and recovered in a metastable state at liq.-N temp. by using the nucleators discovered by Evans and a modification of his technique. No appreciable thermal effect that can be assocd. with a phase transition was obsd. on cooling. During the course of the prepn., measurements were made of the melting lines of ice III, IV, V, and VI. The intersections of these lines allows the coordinates of the hitherto unreported triple points III-IV-L and III-VI-L for both H2O and D2O and IV-VI-L for H2O to be obtained as well as new values of the coordinates of known triple points. The equil. pressure pe of a 1st-order phase transformation is given by pe = -ΔA/ΔV where ΔA and ΔV are the changes of the Helmholtz energy and the vol. at the transition. By using this equation, the effect of isotopic substitution on solid-solid transitions is shown to be caused by the change of vibration frequencies at a transition and for the phases of ice is largely caused by the change of the zero-point energy of the vibrations.
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  Bridgman, P. W. The Pressure-Volume-Temperature Relations of the Liquid, and the Phase Diagram of Heavy Water. J. Chem. Phys. 1935, 3, 597– 605, DOI: 10.1063/1.1749561
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  The pressure-volume-temperature relations of the liquid, and the phase diagram of heavy water
  Bridgman, P. W.
  Journal of Chemical Physics (1935), 3 (), 597-605CODEN: JCPSA6; ISSN:0021-9606.
  The p-v-t relations of both liquid D2O and H2O were detd. by the sylphon method (C. A. 25, 2889; 27, 3127) from -20° to 95° and up to 12,000 kg./sq. cm., and the transition parameters in the range -60° to +20° and up to about 9000 kg./sq. cm. An unstable modification of solid D2O, designated IV, was found in the field of stability of phase V. The corresponding modification of H2O also exists (C. A. 6, 1084). In general the properties of H2O and of D2O covered by these measurements are very much alike, and differ in the direction suggested by the greater zero-point energy of H2O: the molar vol. of D2O is always greater than that of H2O at the same pressure and temp., and the transition lines of D2O always run at higher temps. In finer detail, however, the differences between the two waters do not vary regularly, and probably other considerations than of zero-point energy alone are necessary for a complete explanation.
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  Kagi, H.; Lu, R.; Davidson, P.; Goncharov, A. F.; Mao, H. K.; Hemley, R. J. Evidence for Ice VI as an Inclusion in Cuboid Diamonds from High P-T Near Infrared Spectroscopy. Mineral. Mag. 2000, 64, 1089– 1097, DOI: 10.1180/002646100549904
  There is no corresponding record for this reference.
9. 9
  Tschauner, O.; Huang, S.; Greenberg, E.; Prakapenka, V. B.; Ma, C.; Rossman, G. R.; Shen, A. H.; Zhang, D.; Newville, M.; Lanzirotti, A. Ice-VII Inclusions in Diamonds: Evidence for Aqueous Fluid in Earth’s Deep Mantle. Science 2018, 359, 1136– 1139, DOI: 10.1126/science.aao3030
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  Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth's deep mantle
  Tschauner, O.; Huang, S.; Greenberg, E.; Prakapenka, V. B.; Ma, C.; Rossman, G. R.; Shen, A. H.; Zhang, D.; Newville, M.; Lanzirotti, A.; Tait, K.
  Science (Washington, DC, United States) (2018), 359 (6380), 1136-1139CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
  Water-rich regions in Earth's deeper mantle are suspected to play a key role in the global water budget and the mobility of heat-generating elements. We show that ice-VII occurs as inclusions in natural diamond and serves as an indicator for such water-rich regions. Ice-VII, the residue of aq. fluid present during growth of diamond, crystallizes upon ascent of the host diamonds but remains at pressures as high as 24 gigapascals; it is now recognized as a mineral by the International Mineralogical Assocn. In particular, ice-VII in diamonds points toward fluid-rich locations in the upper transition zone and around the 660-km boundary.
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  Smit, K. V.; Shirey, S. B. Diamonds Help Solve the Enigma of Earth’s Deep Water. Gems Gemol. 2018, 54, 220– 223
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  Consolmagno, G. J. Ice-Rich Moons and the Physical Properties of Ice. J. Phys. Chem. A 1983, 87, 4204– 4208, DOI: 10.1021/j100244a045
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  Warren, S. G. Optical Constants of Ice from the Ultraviolet to the Microwave. Appl. Opt. 1984, 23, 1206– 1225, DOI: 10.1364/AO.23.001206
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  Optical constants of ice from the ultraviolet to the microwave
  Warren, Stephen G.
  Applied Optics (1984), 23 (8), 1206-25CODEN: APOPAI; ISSN:0003-6935.
  A review with 59 refs. A compilation of the optical consts. of ice Ih is made for temps. within 60 K of the m.p. The imaginary part mim of the complex index of refraction m was obtained from measurements of spectral absorption coeff.; the real part mre was computed to be consistent with mim by use of known dispersion relations. The compilation of mim requires subjective interpolation in the near-UV and microwave, a temp. correction in the far-IR, and a choice between 2 conflicting sources in the near-IR. New measurements of the spectral absorption coeff. of pure ice are needed, at temps. near the m.p., for 185-400-nm, 1.4-2.8-μm, 3.5-4.3 μm, 33-600-μm, and 1-100-mm wavelengths.
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  Warren, S. G.; Brandt, R. E. Optical Constants of Ice from the Ultraviolet to the Microwave: A Revised Compilation. J. Geophys. Res. 2008, 113, D14220 DOI: 10.1029/2007JD009744
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14. 14
  Bertie, J. E.; Whalley, E. Infrared Spectra of Ices II, III, and V in the Range 4000 to 350 cm^–1. J. Chem. Phys. 1964, 40, 1646– 1659, DOI: 10.1063/1.1725374
  14
  Infrared spectra of ices II, III, and V in the range 4000 to 350 cm.-1
  Bertie, J. E.; Whalley, E.
  Journal of Chemical Physics (1964), 40 (6), 1646-59CODEN: JCPSA6; ISSN:0021-9606.
  The infrared spectra of ices II, III, and V between 4000 and 350 cm.-1 have been obtained. The ices were made at appropriate pressures and temperatures, cooled under pressure to liquid-nitrogen temperature, and removed from the pressure vessel. Mulls were made near liquid-nitrogen temperature by using isopentane or perfluoropropane as mulling agents, and the spectra of the mulls at ∼100°K. were recorded. The spectra of ices made from H2O, D2O, 5% H2O in D2O, 5% D2O in H2O, and, for ices II and III, 1% D2O in H2O were obtained. In general features, the spectra of pure H2O and D2O ices II, III, and V are similar to those of ice I. For most bands there is a shift of frequency from that in ice I towards the vapor frequencies, but the shift is small compared with the shift between ice I and the vapor. Ices II, III, and V are, therefore, essentially fully hydrogen bonded and are probably four coordinated. This agrees with a proposed structure for ice III. In ices II and III the bands due to the O-H and the O-D stretching vibrations of HDO in dilute solution in D2O and H2O, respectively, show a good deal of fine structure, and are quite narrow, the half-width of the O-D bands being about 5 cm.-1 These are by far the sharpest O-H (or O-D) stretching vibrations of hydrogen-bonded O-H-O groups so far observed. Clearly, breadth is not inherent in the O-H stretching bands of O-H-O. There is also a good deal of fine structure in the bands due to rotational vibrations of water molecules in ices II and III, and much of this fine structure broadens and weakens when a small amount of H2O is added to D2O, and of D2O to H2O. The only simple explanation of this, and of the fine structure of the O-H stretching bands, is that the hydrogen atoms in ices II and III are ordered. No corresponding fine structure occurs in ice V, and the hydrogen atoms are probably disordered, as in ice I.
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15. 15
  Engelhardt, H.; Whalley, E. The Infrared Spectrum of Ice IV in the Range 4000-400 cm^–1. J. Chem. Phys. 1979, 71, 4050– 4051, DOI: 10.1063/1.438173
  15
  The infrared spectrum of ice IV in the range 4000-400 cm-1
  Engelhardt, H.; Whalley, E.
  Journal of Chemical Physics (1979), 71 (10), 4050-1CODEN: JCPSA6; ISSN:0021-9606.
  The IR spectrum of ice IV was recorded in the range 400-4000 cm-1. The location and breadth of the bands confirm that the H2O mols. in ice IV are moderately strongly hydrogen bonded, as they are in the other phases of ice, and are orientationally disordered.
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16. 16
  Bertie, J. E.; Labbe, H. J.; Whalley, E. Infrared Spectrum of Ice VI in the Range 4000 - 50 cm^-1. J. Chem. Phys. 1968, 49, 2141– 2144, DOI: 10.1063/1.1670377
  16
  Infrared spectrum of ice VI in the range 4000-50 cm.-1
  Bertie, J. E.; Labbe, H. J.; Whalley, E.
  Journal of Chemical Physics (1968), 49 (5), 2141-4CODEN: JCPSA6; ISSN:0021-9606.
  The ir spectrum of ice VI recovered at liq.-N temp. and atm. pressure has been investigated in the range 4000-50 cm.-1 The spectrum closely resembles that of ice V, and shows conclusively that ice VI is orientationally disordered when recovered in this way.
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17. 17
  Bertie, J. E.; Labbe, H. J.; Whalley, E. Far-Infrared Spectra of Ice II, V and IX. J. Chem. Phys. 1968, 49, 775– 780, DOI: 10.1063/1.1670138
  17
  Far-infrared spectra of ice II, V, and IX
  Bertie, J. E.; Labbe, H. J.; Whalley, E.
  Journal of Chemical Physics (1968), 49 (2), 775-80CODEN: JCPSA6; ISSN:0021-9606.
  The far-ir spectra of ice II, V, and IX as recovered at liq.-N temp. and atm. pressure have been obtained in the range 360-20 cm.-1 to complement an earlier investigation in the range 4000-350 cm.-1 The bands of ice II and IX are sharp, as is characteristic of ordered crystals, whereas those of ice V are broad, as is characteristic of orientationally disordered crystals. These observations agree with previous conclusions about these phases.
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18. 18
  Minčeva-Śukarova, B.; Sherman, W. F.; Wilkinson, G. R. A High-Pressure Spectroscopic Study of the Ice III - Ice IX, Disordered - Ordered Transition. J. Mol. Struct. 1984, 115, 137– 140, DOI: 10.1016/0022-2860(84)80033-2
  18
  A high pressure spectroscopic study on the ice III-ice IX, disordered-ordered transition
  Minceva-Sukarova, B.; Sherman, W. F.; Wilkinson, G. R.
  Journal of Molecular Structure (1984), 115 (), 137-40CODEN: JMOSB4; ISSN:0022-2860.
  The only published data on the disordered-to-ordered ice III to ice IX transition refers to measurements of dielec. const. Raman spectra of ice III and ice IX were recorded under a pressure of 0.3 GPa for temps. of 130-250 K. They clearly show a transition that is predominantly of the disordered-ordered type. Raman spectra in the frequency range 15-4000 cm-1 are shown, but special attention is given to 2 translational lattice modes at ∼190 cm-1 and 65.5 cm-1 which show somewhat unusual behavior. Small discontinuities in the frequency vs. temp. plots suggest that there is a small discontinuous decrease in the vol. during the ice III to the ice IX transition.
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19. 19
  Minčeva-Śukarova, B.; Sherman, W. F.; Wilkinson, G. R. The Raman Spectra of Ice (I_h, II, III, V, VI and IX) as Functions of Pressure and Temperature. J. Phys. C: Solid State Phys. 1984, 17, 5833– 5850, DOI: 10.1088/0022-3719/17/32/017
  19
  The Raman spectra of ice (Ih, II, III, V, VI and IX) as functions of pressure and temperature
  Minceva-Sukarova, B.; Sherman, W. F.; Wilkinson, G. R.
  Journal of Physics C: Solid State Physics (1984), 17 (32), 5833-50CODEN: JPSOAW; ISSN:0022-3719.
  The Raman spectra of various forms of ice Ih, II, III, IX, V and VI of H2O, D2O, H218O and small percentages of HOD in both D2O and H2O were recorded in their true regions of stability. The high-pressure low-temp. Raman cell used for this work is described. The influence of pressure on the OH and OD stretching modes and the lattice vibrational frequencies is discussed. It is estd. that the pressure compresses the O-O bond lengths on av. about 5 pm-GPa-1 in the Ih, II, III and V types of ice. An attempt was made to correlate the available spectroscopic and crystallog. data for the various forms of ice to make assignments of the Raman- and IR-active lattice vibrational spectra.
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20. 20
  Salzmann, C. G.; Kohl, I.; Loerting, T.; Mayer, E.; Hallbrucker, A. Raman Spectroscopic Study on Hydrogen Bonding in Recovered Ice IV. J. Phys. Chem. B 2003, 107, 2802– 2807, DOI: 10.1021/jp021534k
  20
  Raman Spectroscopic Study on Hydrogen Bonding in Recovered Ice IV
  Salzmann, Christoph G.; Kohl, Ingrid; Loerting, Thomas; Mayer, Erwin; Hallbrucker, Andreas
  Journal of Physical Chemistry B (2003), 107 (12), 2802-2807CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
  Ice IV was prepd. in a reproducible manner on heating high-d. amorphous ice (HDA) at pressure of 0.81 GPa up to ≈162 K at a slow rate of ≈0.5 K min-1, quenching thereafter to 77 K, and recovering the sample under liq. N2 at 1 bar. Recovered ice IV was characterized by x-ray diffraction and it was free of HDA or of low-d. amorphous ice. D2O ice IV contained no cryst. impurities, whereas the HO sample contained a minor impurity of ice XII. D2O ice IV with 11 mol % HOD and HO ice IV with 9.0 mol % HOD were studied in vacuo by Raman spectroscopy between 80 and 145 K. The decoupled O-D (O-H) stretching band in H2O (D2O) ice IV consists of two overlapping peaks centered at 2500(3390) and 2458(3322) cm-1 at 80 K. Peak max. of the coupled O-H (O-D) stretching band region is at 3200(2360) cm-1. At low frequency a band at ≈498 (≈365) cm-1 is assigned to a librational mode, whereas bands at ≈252 (≈250), 208(203), 178(172), 152(149) and 126(123) cm-1 originate from translation modes. On heating ice IV, the authors measured the development of peak-positions and the phase transition from ice IV to ice I. The authors did not observe indication for formation of an amorphous phase during this transition. Curve resoln. of the decoupled O-D stretching transition region into two component bands is consistent with the assignment of the high-frequency band centered at 2500 cm-1 to the O-D···O H-bonds with 2.88 and 2.92 Å length, and of the low-frequency component band centered at 2458 cm-1 to H-bonds with 2.79 and 2.81 Å length. The composite band shape is consistent with large fwhh's (full width at half-heights) of the distinct bands from the four types of H-bonds.
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21. 21
  Salzmann, C.; Kohl, I.; Loerting, T.; Mayer, E.; Hallbrucker, A. The Raman Spectrum of Ice XII and Its Relation to That of a New “High-Pressure Phase of H₂O Ice”. J. Phys. Chem. B 2002, 106, 1– 6, DOI: 10.1021/jp012755d
  21
  The Raman Spectrum of Ice XII and Its Relation to that of a New "High-Pressure Phase of H2O Ice"
  Salzmann, Christoph; Kohl, Ingrid; Loerting, Thomas; Mayer, Erwin; Hallbrucker, Andreas
  Journal of Physical Chemistry B (2002), 106 (1), 1-6CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)
  By comparison of Raman spectra probably the new high-pressure phase of H2O ice reported by Chou et al. (Science 1998, 281, 809) is in fact ice XII. Pure ice XII was prepd. in a reproducible manner on heating high-d. amorphous ice (HDA) at a pressure of 0.81 GPa up to ≈180 K at a rate of 25 K min-1, quenching thereafter to 77 K, and recovering the sample under liq. N2 at 1 bar. Recovered ice XII was characterized by x-ray diffraction and it was free of HDA, of low-d. amorphous ice, and of ice IV. H2O ice XII contg. 11 mol % HOD and D2O ice XII with 9.0 mol % HDO were studied by Raman spectroscopy between 80 and 150 K. The decoupled O-D (O-H) stretching band in H2O (D2O) ice XII consists of a nearly sym. band, slightly skewed at low frequency, which is centered at 80 K at 2473 (≈3340) cm-1, with full-width at half-height (fwhh) of 44 (≈80) cm-1. At low frequency a broad band at ≈470 (≈360) cm-1 and a sharp band at 195(190) cm-1 are assigned to the librational and translational mode in H2O (D2O) ice XII. The main feature of the decoupled O-D stretching band is attributed to the H bonds with O-D-O distance of 2.803 Å and multiplicity 6 obtained from neutron diffraction. The 2nd O-D-O distance of 2.766 Å with multiplicity 2 is expected to give a decoupled O-D component peak sepd. only ≈28 cm-1 from the main peak. These two component bands would appear as distinct peaks only when their fwhh is small, that is when ice XII is proton ordered. However, the composite band shape is consistent with large fwhh and proton disorder in ice XII. The authors did not observe indication for formation of an amorphous phase as intermediate on the ice XII → cubic ice phase transition, which is consistent with the authors' previous x-ray diffraction study. However, the results are in conflict with a recent report of the Raman spectrum of ice XII and of formation of amorphous ice on careful annealing of ice XII by Tulk and Klug (Phys. Rev. B 2001, 63, 212201-1).
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22. 22
  Salzmann, C. G.; Hallbrucker, A.; Finney, J. L.; Mayer, E. Raman Spectroscopic Features of Hydrogen-Ordering in Ice XII. Chem. Phys. Lett. 2006, 429, 469– 473, DOI: 10.1016/j.cplett.2006.08.079
  22
  Raman spectroscopic features of hydrogen-ordering in ice XII
  Salzmann, Christoph G.; Hallbrucker, Andreas; Finney, John L.; Mayer, Erwin
  Chemical Physics Letters (2006), 429 (4-6), 469-473CODEN: CHPLBC; ISSN:0009-2614. (Elsevier B.V.)
  The Raman spectra of recovered H ordered H2O and D2O ice XIV were recorded and compared with the spectra of the corresponding H disordered phase (ice XII). On heating ice XIV, the transition to ice XII is obsd. Subsequent cooling leads to the weak reappearance of ice XIV lattice vibrational peaks which demonstrates the reversibility of the H order ↹ disorder phase transition. However, cooling at ambient pressure produces a less ordered ice XIV than cooling under pressure which implies that pressure favors H ordering of ice XII.
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23. 23
  Salzmann, C. G.; Hallbrucker, A.; Finney, J. L.; Mayer, E. Raman Spectroscopic Study of Hydrogen Ordered Ice XIII and of Its Reversible Phase Transition to Disordered Ice V. Phys. Chem. Chem. Phys. 2006, 8, 3088– 3093, DOI: 10.1039/b604360g
  23
  Raman spectroscopic study of hydrogen ordered ice XIII and of its reversible phase transition to disordered ice V
  Salzmann, Christoph G.; Hallbrucker, Andreas; Finney, John L.; Mayer, Erwin
  Physical Chemistry Chemical Physics (2006), 8 (26), 3088-3093CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
  Raman spectra of recovered ordered H2O (D2O) ice XIII doped with 0.01 M HCl (DCl) recorded in vacuo at 80 K are reported in the range 3600-200 cm-1. The bands are assigned to the various types of modes from isotope ratios. On thermal cycling between 80 and 120 K, the reversible phase transition to disordered ice V is obsd. The remarkable effect of HCl (DCl) on orientational ordering in ice V and its phase transition to ordered ice XIII, 1st reported in a powder neutron diffraction study of DCl doped D2O ice V (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758), is demonstrated by Raman spectroscopy and discussed. The dopants KOH and HF have only a minor effect on H ordering in ice V, as shown by the Raman spectra.
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24. 24
  Whale, T. F.; Clark, S. J.; Finney, J. L.; Salzmann, C. G. DFT-Assisted Interpretation of the Raman Spectra of Hydrogen-Ordered Ice XV. J. Raman Spectrosc. 2013, 44, 290– 298, DOI: 10.1002/jrs.4170
  24
  DFT-assisted interpretation of the Raman spectra of hydrogen-ordered ice XV
  Whale, Thomas F.; Clark, Stewart J.; Finney, John L.; Salzmann, Christoph G.
  Journal of Raman Spectroscopy (2013), 44 (2), 290-298CODEN: JRSPAF; ISSN:0377-0486. (John Wiley & Sons Ltd.)
  The vibrational spectra of the condensed phases of water often show broad and strongly overlapping spectral features which can make spectroscopic interpretations and peak assignments difficult. The Raman spectra of hydrogen-ordered H2O and D2O ice XV are reported here, and it is shown that the spectra can be fully interpreted in terms of assigning normal modes to the various spectral features by using d. functional theory (DFT) calcns. The calcd. lattice-vibration spectrum of the exptl. antiferroelec. P1 structure is in good agreement with the exptl. data whereas the spectrum of a ferroelec. Cc structure, which computational studies have suggested as the crystal structure of ice XV, differs substantially. Moreover, the calcd. P1 coupled O-H stretch spectrum also seems in better agreement with the expt. than the calcd. spectrum for the Cc structure. Both the hydrogen bonds as well as the covalent bonds appear to be stronger in hydrogen-ordered ice XV than in the hydrogen-disordered counterpart ice VI. A new type of stretching mode is identified, and it is speculated that this kind of mode might be relevant for other condensed water phases as well. Furthermore, the ice XV spectra are compared to the spectra of ice VIII which is the only other high-pressure phase of ice for which detailed spectroscopic assignments have been made so far. In summary, we have established a link between crystallog. data and spectroscopic information in the case of ice XV by using DFT-calcd. spectra. Such correlations may eventually help interpreting the vibrational spectra of more structurally-disordered aq. systems.
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25. 25
  Thoeny, A. V.; Gasser, T. M.; Loerting, T. Distinguishing Ice β-XV from Deep Glassy Ice VI: Raman Spectroscopy. Phys. Chem. Chem. Phys. 2019, 21, 15452– 15462, DOI: 10.1039/C9CP02147G
  25
  Distinguishing ice β-XV from deep glassy ice VI: Raman spectroscopy
  Thoeny, Alexander V.; Gasser, Tobias M.; Loerting, Thomas
  Physical Chemistry Chemical Physics (2019), 21 (28), 15452-15462CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
  The nature of the hydrogen sublattice of an HCl-doped ice VI sample after cooling at 1.8 GPa has been a topic of recent interest. The samples are interpreted either as the new H-ordered ice phase ice β-XV with a thermodn. stability region in the phase diagram [T. M. Gasser et al., Chem. Sci., 2018, 9, 4224], or alternatively as H-disordered, deep glassy ice VI [A. Rosu-Finsen and C. G. Salzmann, Chem. Sci., 2019, 10, 515]. Here we provide a comprehensive Raman spectroscopic study on ice β-XV, ice XV and ice VI, with the following key findings: (i) the Raman spectra of ice β-XV differ fundamentally from those of ice VI and ice XV, where the degree of H-order is even higher than in ice XV. (ii) Upon cooling ice VI there is competition between formation of ice XV and ice β-XV domains, where ice XV forms at 0.0 GPa, but ice β-XV at 1.8 GPa. Domains of ice β-XV are present in literature "ice XV" at 1.0 GPa. This result clarifies the puzzling earlier observation that the degree of H-order in ice XV apparently improves upon heating and recooling at ambient pressure. In reality, this procedure leaves the H-order in ice XV unaffected, but removes ice β-XV domains by transforming them to ice XV. (iii) Upon heating, the samples experience the transition sequence ice β-XV → ice XV → ice VI, i.e., an order-order transition at 103 K followed by an order-disorder transition at 129 K. The former progresses via a disordered transient state. (iv) D2O ice β-XV forms upon cooling DCl-doped D2O-ice VI, albeit at a much lower pace than in the hydrogenated case so that untransformed D2O ice VI domains are present even after slow cooling. The librational band at 380 cm-1 is identified to be the characteristic spectroscopic feature of deuterated ice β-XV. Taken together these findings clarify open questions in previous work on H-ordering in the ice VI lattice, rule out a glassy nature of ice β-XV and pave the way for a future neutron diffraction study to refine the crystal structure of D2O ice β-XV.
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26. 26
  Clark, R. N. Water Frost and Ice - the Near Infrared Spectral Reflectance at 0.65–2.5 μm. J. Geophys. Res. 1981, 86, 3087– 3096, DOI: 10.1029/JB086iB04p03087
  26
  Water frost and ice: the near-infrared spectral reflectance 0.65-2.5 μm
  Clark, Roger N.
  Journal of Geophysical Research, B (1981), 86 (B4), 3087-96CODEN: JJGBDU; ISSN:0196-6936.
  The spectral reflectance of H2O frost and frost on ice as a function of temp. and grain size is presented with 11/2% spectral resoln. in the 0.65- to 2.5-μm wavelength region. The well-known 2.0-, 1.65-, and 1.5-μm solid H2O absorption bands are precisely defined along with the little studied 1.25-μm band and the previously unidentified (in reflectance) 1.04-, 0.90-, and 0.81-μm absorption bands. The 1.5-μm band complex is quant. analyzed using a nonlinear least squares algorithm to resolve the band into 4 Gaussian components as a function of grain size and temp. The 1.65-μm component, which was thought to be a good temp. sensor, is highly grain size dependent and poorly suited to temp. sensing. Another Gaussian component appears to show a dependence of width on grain size while being independent of temp. The relative apparent band depths are different for frost layers on ice than for thick layers of frost and may explain the apparent band depths seen in many planetary reflectance spectra.
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27. 27
  Grundy, W. M.; Schmitt, B. The Temperature-Dependent Near-Infrared Absorption Spectrum of Hexagonal H₂O Ice. J. Geophys. Res. 1998, 103, 25809– 25822, DOI: 10.1029/98JE00738
  27
  The temperature-dependent near-infrared absorption spectrum of hexagonal H2O ice
  Grundy, W. M.; Schmitt, B.
  Journal of Geophysical Research, [Planets] (1998), 103 (E11), 25809-25822CODEN: JGPLEH; ISSN:1934-8592. (American Geophysical Union)
  Transmission spectra were measured between 1.0 and 2.7 μm for monocryst. samples of hexagonal water ice at temps. between 20 and 270 K. Samples were crystd. from liq. water within closed cells, with thicknesses ranging from 100 μm to 1.0 cm. The absorption spectrum of ice changes with temp. in several ways. With higher temp., the shapes of absorption bands become more smoothed, the strengths of some absorption bands decrease, the absorption in continuum wavelengths increases, and the band centers of some absorption bands shift to shorter wavelengths. In this paper we present the new absorption coeff. spectra along with an examn. of the different temp. effects. These data should prove extremely valuable for anal. of near-IR reflectance spectra of low-temp. icy surfaces, such as those of outer solar system satellites, Kuiper Belt objects, Pluto and Charon, comet nuclei, the polar caps of Mars, and terrestrial snow- and ice-covered regions. The data may also be of value in simulating radiative transfer in clouds of ice particles in the atmospheres of planets.
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28. 28
  Leto, G.; Gomis, O.; Strazzulla, G. The Reflectance Spectrum of Water Ice: Is the 1.65 μm Peak a Good Temperature Probe?. Mem. Soc. Astron. Ital. Suppl. 2005, 6, 57– 62
  There is no corresponding record for this reference.
29. 29
  Tonauer, C. M.; Seidl-Nigsch, M.; Loerting, T. High-Density Amorphous Ice: Nucleation of Nanosized Low-Density Amorphous Ice. J. Phys.: Condens. Matter 2018, 30, 034002 DOI: 10.1088/1361-648X/aa9e76
  29
  High-density amorphous ice: nucleation of nanosized low-density amorphous ice
  Tonauer, Christina M.; Seidl-Nigsch, Markus; Loerting, Thomas
  Journal of Physics: Condensed Matter (2018), 30 (3), 034002/1-034002/11CODEN: JCOMEL; ISSN:0953-8984. (IOP Publishing Ltd.)
  The pressure dependence of the crystn. temp. of different forms of expanded high-d. amorphous ice (eHDA) was scrutinized. Crystn. at pressures 0.05- 0.30 GPa was followed using volumetry and powder x-ray diffraction. eHDA samples were prepd. via isothermal decompression of very high-d. amorphous ice at 140 K to different end pressures between 0.07-0.30 GPa (eHDA0.07-0.3). At 0.05-0.17 GPa the crystn. line Tx (p) of all eHDA variants is the same. At pressures >0.17 GPa, all eHDA samples decompressed to pressures <0.20 GPa exhibit significantly lower Tx values than eHDA0.2 and eHDA0.3. We rationalize our findings with the presence of nanoscaled low-d. amorphous ice (LDA) seeds that nucleate in eHDA when it is decompressed to pressures <0.20 GPa at 140 K. Below ∼0.17 GPa, these nanosized LDA domains are latent within the HDA matrix, exhibiting no effect on Tx of eHDA<0.2. Upon heating at pressures ≥0.17 GPa, these nanosized LDA nuclei transform to ice IX nuclei. They are favored sites for crystn. and, hence, lower Tx. By comparing crystn. expts. of bulk LDA with the ones involving nanosized LDA we are able to est. the Laplace pressure and radius of ∼0.3-0.8 nm for the nanodomains of LDA. The nucleation of LDA in eHDA revealed here is evidence for the first-order-like nature of the HDA → LDA transition, supporting water's liq.-liq. transition scenarios.
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30. 30
  Mishima, O.; Endo, S. Phase Relations of Ice under Pressure. J. Chem. Phys. 1980, 73, 2454– 2456, DOI: 10.1063/1.440396
  30
  Phase relations of ice under pressure
  Mishima, O.; Endo, S.
  Journal of Chemical Physics (1980), 73 (5), 2454-6CODEN: JCPSA6; ISSN:0021-9606.
  The transitions between various ice polymorphs were obsd. with a manganin sensor under pressure. The stable region of ice V disappeared at low temp. and the direct transition from ice II to ice VI was obsd. The triple point of ice II, V, and VI exists in the neighborhood of -60° and 6 kbar. The P-T phase diagram of H2O was constructed.
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31. 31
  Shephard, J. J.; Salzmann, C. G. The Complex Kinetics of the Ice VI to Ice XV Hydrogen Ordering Phase Transition. Chem. Phys. Lett. 2015, 637, 63– 66, DOI: 10.1016/j.cplett.2015.07.064
  31
  The complex kinetics of the ice VI to ice XV hydrogen ordering phase transition
  Shephard, Jacob J.; Salzmann, Christoph G.
  Chemical Physics Letters (2015), 637 (), 63-66CODEN: CHPLBC; ISSN:0009-2614. (Elsevier B.V.)
  The reversible phase transition from hydrochloric-acid-doped ice VI to its hydrogen-ordered counterpart ice XV is followed using differential scanning calorimetry. Upon cooling at ambient pressure fast hydrogen ordering is obsd. at first followed by a slower process which manifests as a tail to the initial sharp exotherm. The residual hydrogen disorder in H2O and D2O ice XV is detd. as a function of the cooling rate. We conclude that it will be difficult to obtain fully hydrogen-ordered ice XV by cooling at ambient pressure. Our new exptl. findings are discussed in the context of recent computational work on ice XV.
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32. 32
  Mishima, O.; Calvert, L. D.; Whalley, E. ″Melting Ice″ I at 77 K and 10 kbar: A New Method of Making Amorphous Solids. Nature 1984, 310, 393– 395, DOI: 10.1038/310393a0
  32
  'Melting ice' I at 77 K and 10 kbar: a new method of making amorphous solids
  Mishima, O.; Calvert, L. D.; Whalley, E.
  Nature (London, United Kingdom) (1984), 310 (5976), 393-5CODEN: NATUAS; ISSN:0028-0836.
  A new way is reported of prepg. an amorphous solid, by melting a solid by pressure below the glass transition of the liq., and it is applied to making a new kind of amorphous ice. Thus, ice I was transformed to an amorphous phase, as detd. by x-ray diffraction, by pressurizing it at 77 K to its extrapolated m.p. of 10 kbar. At the m.p., the fluid is well below its glass transition. On heating at a rate of ∼2.6 K min-1 at zero pressure it transforms at ∼117 K to a 2nd amorphous phase with a heat evolution of 42 ± ∼8 J g-1, and at ∼152 K further transforms to ice I with a heat evolution of 92 ± ∼15 J g-1. In 1 sample, ice Ic was formed and in another, existing crystals of ice Ih grew from the amorphous phase. Heating below the 117 K transition causes irreversible changes in the diffraction pattern, and a continuous range of amorphous phases can be made. Similar transformations will probably occur in all solids whose m.p. decreases with increasing pressure if they can be cooled sufficiently for a transformation to a cryst. solid to be too slow.
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33. 33
  Petrenko, V. F.; Whitworth, R. W. Physics of Ice; Oxford University Press: Oxford, 1999.
  There is no corresponding record for this reference.
34. 34
  Bertie, J. E.; Whalley, E. Infrared Spectra by Mulling Techniques at Liquid Nitrogen Temperatures. Spectrochim. Acta 1964, 20, 1349– 1356, DOI: 10.1016/0371-1951(64)80115-6
  34
  Infrared spectra by mulling techniques at liquid-nitrogen temperatures
  Bertie, J. E.; Whalley, E.
  Spectrochimica Acta (1964), 20 (9), 1349-56CODEN: SPACA5; ISSN:0038-6987.
  An exptl. technique is described for making spectroscopic mulls near liquid-N temps. This technique allows such materials to be examd. spectroscopically and the phase to be verified relatively easily by x-ray diffraction. The most useful mulling agents are propane, propylene, and chlorotrifluoromethane. Perfluoropropane and isopentane are possible mulling agents, but are not as useful as those mentioned above because their m.ps. are rather high.
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35. 35
  Bertie, J. E.; Whalley, E. Infrared Spectra of Ices I_h and I_c in the Range 4000 to 350 cm^–1. J. Chem. Phys. 1964, 40, 1637– 1645, DOI: 10.1063/1.1725373
  37
  Infrared spectra of ices Ih and Ic in the range 4000 to 350 cm.-1
  Bertie, J. E.; Whalley, E.
  Journal of Chemical Physics (1964), 40 (6), 1637-45CODEN: JCPSA6; ISSN:0021-9606.
  The infrared spectra of ice Ih made from H2O, D2O, a mixt. of 95% H2O and 5% D2O, and a mixt. of 5% H2O and 95% D2O, and of ice Ic made from H2O, D2O, and a mixt. of 95% H2O and 5% D2O, were recorded in the region 4000 to 350 cm.-1 by using low-temp. mulling techniques. The ice Ic was made by the transformation of ices II and III, and was authenticated by its x-ray diffraction powder pattern. The spectra of ices Ih and Ic are identical, within exptl. error. The spectra of ice Ih, while similar in their main features to those reported by earlier workers, differ significantly in detail, probably largely because much of the previous work, particularly on D2O ice, was done with partly vitreous ice. The usual interpretation of the bands in terms of the ν1, ν2, ν3, and νR vibrations of isolated mols. is greatly oversimplified because intermol. coupling is important. There are at least 6 (5 infrared and one Raman) bands due to O-D stretching vibrations in the spectrum of D2O ice I, but the detailed origin is unknown. The breadth of the O-H and O-D stretching bands of HDO in dil. soln. in D2O and H2O is interpreted as indicating a disarrangement of the O positions due to the disorder of the H atoms.
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36. 36
  Kubelka, P.; Munk, F. An Article on Optics of Paint Layers. Fuer Tekn. Phys. 1931, 12, 593– 609
  There is no corresponding record for this reference.
37. 37
  Torrent, J.; Barron, V. Diffuse Reflectance Spectroscopy; American Society of Agronomy and Soil Science: Madison, WI, 2015.
  There is no corresponding record for this reference.
38. 38
  Rajaram, B.; Glandorf, D. L.; Curtis, D. B.; Tolbert, M. A.; Toon, O. B.; Ockman, N. Temperature-Dependent Optical Constants of Water Ice in the near Infrared: New Results and Critical Review of the Available Measurements. Appl. Opt. 2001, 40, 4449– 4462, DOI: 10.1364/AO.40.004449
  38
  Temperature-dependent optical constants of water ice in the near infrared: new results and critical review of the available measurements
  Rajaram B; Glandorf D L; Curtis D B; Tolbert M A; Toon O B; Ockman N
  Applied optics (2001), 40 (25), 4449-62 ISSN:1559-128X.
  The optical constants of water ice have been determined in the near infrared from 4000 to 7000 cm(-1). Polycrystalline ice films with thickness as great as ~1164 mum were formed by condensation of water vapor on a cold silicon substrate at temperatures of 166, 176, 186, and 196 K. The transmission of light through the ice films was measured during their growth from 0 to 1164 mum over the frequency range of approximately 500-7000 cm(-1). The optical constants were extracted by means of simultaneously fitting the calculated transmission spectra of films of varying thickness to their respective measured transmission spectra with an iterative Kramers-Kronig technique. Equations are presented to account for reflection losses at the interfaces when the sample is held in a cell. These equations are used to reanalyze the transmission spectrum of water ice (358-mum sample at 247 K) recorded by Ockman in 1957 [Philos. Mag. Suppl. 7, 199 (1958)]. Our imaginary indices for water ice are compared with those of Gosse et al. [Appl. Opt. 34, 6582 (1995)], Kou et al. [Appl. Opt. 32, 3531 (1993)], Grundy and Schmitt [J. Geophys. Res. 103, 25809 (1998)], and Warren [Appl. Opt. 23, 1206 (1984)], and with the new indices from Ockman's spectrum. The temperature dependence in the imaginary index of refraction observed by us between 166 and 196 K and that between our data at 196 K and the data of Gosse et al. at 250 K are compared with that predicted by the model of Grundy and Schmitt. On the basis of this comparison a linear interpolation of the imaginary indices of refraction between 196 and 250 K is proposed. We believe that the accuracy of this interpolation is better than 20%.
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39. 39
  Ockman, N. The Infrared and Raman Spectra of Ice. Adv. Phys. 1958, 7, 199– 220, DOI: 10.1080/00018735800101227
  39
  The infrared and Raman spectra of ice
  Ockman, Nathan
  (1958), 7 (), 199-220 ISSN:.
  A review with bibliography.
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40. 40
  Ockman, N.; Sutherland, G. B. B. M. Infrared and Raman Spectra of Single Crystals of Ice. Proc. R. Soc. London 1958, 247, 434– 440, DOI: 10.1098/rspa.1958.0198
  40
  Infrared and Raman spectra of single ice crystals
  Ockman, N.; Sutherland, G. B. B. M.
  Proceedings of the Royal Society of London, Series A: Mathematical, Physical and Engineering Sciences (1958), 247 (), 434-40CODEN: PRLAAZ; ISSN:1364-5021.
  The infrared dichroism of single crystals of ice is not a very sensitive criterion for distinguishing among proposals about the location of H atoms in ice. The absence of dichroism in the fundamental frequencies eliminates 3 out of 7 proposed models. Only the Owston model (CA 48, 7383g) is completely excluded.
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41. 41
  Larsen, C. F.; Williams, Q. Overtone Spectra and Hydrogen Potential of H₂O at High Pressure. Phys. Rev. B 1998, 58, 8306– 8312, DOI: 10.1103/PhysRevB.58.8306
  41
  Overtone spectra and hydrogen potential of H2O at high pressure
  Larsen, Christopher F.; Williams, Quentin
  Physical Review B: Condensed Matter and Materials Physics (1998), 58 (13), 8306-8312CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
  The 1st overtones of the stretching and bending vibrations of H2O and the 1st stretching overtone of D2O pressures of 37 GPa at 300 K, encompassing the stability fields of H2O, ice VI, and ice VII. The successive disappearance of the overtone peaks in ice VII with increasing pressure indicates that the barrier height in the double min. H potential decreases at a rate of 230 cm-1 GPa-1 (0.029 eV GPa-1) to pressures of 32 GPa. The 1st overtone of the O-H stretching vibration splits and forms a doublet between 10 and 25 GPa, implying that the barrier height is near the energy of this overtone and that proton tunneling may occur at this energy level between 10 and 25 GPa. The frequency of the 1st stretching overtone of ice VII is also strongly influenced by quantum effects near the barrier top, as its frequency is larger than harmonic values. The H bonding potential in ice VII at high pressure is described using a semiempirical potential model that incorporates the obsd. rate of barrier height redn. and available O-H and O-O bond length data of ice VII under pressure. This model requires a rapid increase in O-H bond length between 40 and 60 GPa to reach a value of 1/2 the O-O distance >60 GPa, at which pressure the transition to ice X was reported to occur. Up to 40 GPa, the model is consistent with the trend of O-H bond length obsd. in neutron diffraction data to 10 GPa.
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42. 42
  Salzmann, C. G.; Radaelli, P. G.; Slater, B.; Finney, J. L. The Polymorphism of Ice: Five Unresolved Questions. Phys. Chem. Chem. Phys. 2011, 13, 18468– 18480, DOI: 10.1039/c1cp21712g
  42
  The polymorphism of ice: five unresolved questions
  Salzmann, Christoph G.; Radaelli, Paolo G.; Slater, Ben; Finney, John L.
  Physical Chemistry Chemical Physics (2011), 13 (41), 18468-18480CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
  A review. Our recent discovery of three new phases of ice has increased the total no. of known distinct polymorphs of ice to fifteen. In this Perspective article, we give a brief account of previous work in the field, and discuss some of the particularly interesting open questions that have emerged from recent studies. These include (i) the effectiveness of acid and base dopants to enable hydrogen-ordering processes in the ices, (ii) the comparison of the calorimetric data of some of the cryst. phases of ice and low-d. amorphous ice, (iii) the disagreement between the exptl. ice XV structure and computational predictions, (iv) the incompleteness of some of the hydrogen order/disorder pairs and (v) the new frontiers at the high and neg. pressure ends of the phase diagram.
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43. 43
  Grundy, W. M.; Buie, M. W.; Stansberry, J. A.; Spencer, J. R.; Schmitt, B. Near-Infrared Spectra of Icy Outer Solar System Surfaces: Remote Determination of H₂O Ice Temperatures. Icarus 1999, 142, 536– 549, DOI: 10.1006/icar.1999.6216
  43
  Near-infrared spectra of icy outer Solar System surfaces: remote determination of H2O ice temperatures
  Grundy, W. M.; Buie, M. W.; Stansberry, J. A.; Spencer, J. R.; Schmitt, B.
  Icarus (1999), 142 (2), 536-549CODEN: ICRSA5; ISSN:0019-1035. (Academic Press)
  We present new 1.20 to 2.35 μm spectra of satellites of Jupiter, Saturn, and Uranus, and the rings of Saturn, obtained in 1995 and 1998 at Lowell Observatory. For most of the target objects, our data provide considerable improvement in spectral resoln. and signal-to-noise over previously published data. Absorption bands with shapes characteristic of low-temp., hexagonal cryst. H2O ice dominate the spectra of most of our targets in this wavelength range. We make use of newly published temp.-dependent wavelengths and relative strengths of H2O absorption bands to infer ice temps. from our spectra. These ice temps. are distinct from temps. detd. from thermal emission measurements or simulations of radiative balances. Unlike those methods, which av. over all terrains including ice-free regions, our temp.-sensing method is only sensitive to the ice component. Our method offers a new constraint which, combined with other observations, can lead to better understanding of thermal properties and textures of remote, icy surfaces. Ice temps. are generally lower than thermal emission brightness temps., indicative of the effects of thermal inertia and segregation between ice and warmer, darker materials. We also present the results of expts. to investigate possible changes of water ice temp. over time, including observations of Titania at two epochs, and of Ganymede and saturnian ring particles following emergence from the eclipse shadows of their primary planets. Finally, we discuss limitations of our temp. measurement method which can result from the presence of H2O in phases other than hexagonal ice-Ih, such as amorphous ice, hydrated mineral phases, or radiation-damaged cryst. ice. Our spectra of Europa and Enceladus exhibit peculiar spectral features which may result from effects such as these. (c) 1999 Academic Press.
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44. 44
  Loerting, T.; Bauer, M.; Kohl, I.; Watschinger, K.; Winkel, K.; Mayer, E. Cryoflotation: Densities of Amorphous and Crystalline Ices. J. Phys. Chem. B 2011, 115, 14167– 14175, DOI: 10.1021/jp204752w
  44
  Cryoflotation: Densities of Amorphous and Crystalline Ices
  Loerting, Thomas; Bauer, Marion; Kohl, Ingrid; Watschinger, Katrin; Winkel, Katrin; Mayer, Erwin
  Journal of Physical Chemistry B (2011), 115 (48), 14167-14175CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
  The authors present an exptl. method aimed at measuring mass densities of solids at ambient pressure. The principle of the method is flotation in a mixt. of liq. N and liq. Ar, where the mixing ratio is varied until the solid hovers in the liq. mixt. The temp. of such mixts. is at 77-87 K, and therefore, the main advantage of the method is the possibility of detg. densities of solid samples, which are instable >90 K. The accessible d. range (∼0.81-1.40 g cm-3) is perfectly suitable for the study of cryst. ice polymorphs and amorphous ices. As a benchmark, the authors here det. densities of cryst. polymorphs (ices Ih, Ic, II, IV, V, VI, IX, and XII) by flotation and compare them with crystallog. densities. The reproducibility of the method is about ±0.005 g cm-3, and in general, the agreement with crystallog. densities is very good. Also, the authors show measurements on a range of amorphous ice samples and correlate the d. with the d spacing of the 1st broad halo peak in diffraction expts. Finally, the influence of microstructure, in particular voids, on the d. for the case of hyperquenched glassy H2O and cubic ice samples prepd. by deposition of micrometer-sized liq. droplets are discussed.
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45. 45
  Herrero, C. P.; Ramirez, R. Topological Characterization of Crystalline Ice Structures from Coordination Sequences. Phys. Chem. Chem. Phys. 2013, 15, 16676– 16685, DOI: 10.1039/c3cp52167b
  45
  Topological characterization of crystalline ice structures from coordination sequences
  Herrero, Carlos P.; Ramirez, Rafael
  Physical Chemistry Chemical Physics (2013), 15 (39), 16676-16685CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
  Topol. properties of cryst. ice structures are studied by considering ring statistics, coordination sequences, and topol. d. of different ice phases. The coordination sequences (no. of sites at topol. distance k from a ref. site) have been obtained by direct enumeration until at least 40 coordination spheres for different ice polymorphs. This allows us to study the asymptotic behavior of the mean no. of sites in the k-th shell, Mk, for high values of k: Mk ∼ ak2, a being a structure-dependent parameter. Small departures from a strict parabolic dependence have been studied by considering first and second differences of the series {Mk} for each structure. The parameter a ranges from 2.00 for ice VI to 4.27 for ice XII, and is used to define a topol. d. for these solid phases of water. Correlations between such topol. d. and the actual vol. of ice phases are discussed. Ices Ih and Ic are found to depart from the general trend in this correlation due to the large void space in their structures.
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Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c09764.
- Powder X-ray diffractograms of each high-pressure ice sample used in the present study; optical microscopy image of a powdered sample of hexagonal ice I_h at 248 K; depiction of the baseline correction procedure deployed; and peak identification based on first and second derivative spectra (PDF)
- Normalized Kubelka–Munk function in % for ices I_h, II, IV, V, VI, IX, and XII is shown in Figures 1 and 2a,b (TXT)
- Raw Kubelka–Munk function spectra of ice I_h (TXT)
- Raw Kubelka–Munk function spectra of ice II (TXT)
- Raw Kubelka–Munk function spectra of ice IV (TXT)
- Raw Kubelka–Munk function spectra of ice V (TXT)
- Raw Kubelka–Munk function spectra of ice VI (TXT)
- Raw Kubelka–Munk function spectra of ice IX (TXT)
- Raw Kubelka–Munk function spectra of ice XII (TXT)
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Near-Infrared Spectra of High-Density Crystalline H₂O Ices II, IV, V, VI, IX, and XII
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Near-Infrared Spectra of High-Density Crystalline H2O Ices II, IV, V, VI, IX, and XIIClick to copy article linkArticle link copied!

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Near-Infrared Spectra of High-Density Crystalline H₂O Ices II, IV, V, VI, IX, and XII
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