Decomposition and Growth Pathways for Ammonium Nitrate Clusters and NanoparticlesClick to copy article linkArticle link copied!
- Ubaidullah S. HassanUbaidullah S. HassanDepartment of Chemistry, Albert Nerken School of Engineering, The Cooper Union for the Advancement of Science and Art, 41 Cooper Square, New York, New York 10003, United StatesMore by Ubaidullah S. Hassan
- Miguel A. AmatMiguel A. AmatDepartment of Chemistry, Albert Nerken School of Engineering, The Cooper Union for the Advancement of Science and Art, 41 Cooper Square, New York, New York 10003, United StatesMore by Miguel A. Amat
- Robert Q. Topper*Robert Q. Topper*Email: [email protected]Department of Chemistry, Albert Nerken School of Engineering, The Cooper Union for the Advancement of Science and Art, 41 Cooper Square, New York, New York 10003, United StatesMore by Robert Q. Topper
Abstract
Understanding the formation and decomposition mechanisms of aerosolized ammonium nitrate species will lead to improvements in modeling the thermodynamics and kinetics of aerosol haze formation. Studying the sputtered mass spectra of cation and anion ammonium nitrate clusters can provide insights as to which growth and evaporation pathways are favored in the earliest stages of nucleation and thereby guide the development and use of accurate models for intermolecular forces for these systems. Simulated annealing Monte Carlo optimization followed by density functional theory optimizations can be used reliably to predict minimum-energy structures and interaction energies for the cation and anion clusters observed in mass spectra as well as for neutral nanoparticles. A combination of translational and rotational mag-walking and sawtooth simulated annealing methods was used to find optimum structures of the various heterogeneous clusters identifiable in the mass spectra. Following these optimizations with ωB97X-D3 density functional theory calculations made it possible to rationalize the pattern of peaks in the mass spectra through computation of the binding energies of clusters involved in various growth and dissociation pathways. Testing these calculations against CCSD(T) and MP2 predictions of the structures and binding energies for small clusters demonstrates the accuracy of the chosen model chemistry. For the first time, the peaks corresponding with all detectable species in both the positive and negative ion mass spectra of ammonium nitrate are identified with their corresponding structures. Thermodynamic control of particle growth and decomposition of ions due to loss of ammonia or nitric acid molecules is indicated. Structures and interaction energies for larger (NH4NO3)n nanoparticles are also presented, including the prediction of new particle morphologies with trigonal pyramidal character.
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License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
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Special Issue
Published as part of The Journal of Physical Chemistry A special issue “Mark A. Johnson Festschrift”.
Introduction
Methods
Figure 1
Figure 1. (NH3–HNO3)and (NH4HNO3)2 structures at the ωB97X-D3/def2-SVPD level of theory.
Model chemistry | D0 | Reference |
---|---|---|
CCSD(T)/CBS//MP2/aug-cc-pVTZb | 48.6 ± 3 | Irikura 2010 (18) |
MP2/CBS//MP2/aug-cc-pVTZ | 48.9 | ″ |
MP2/aug-cc-pVTZ | 48.9 | Present work |
MP2/aug-cc-pVTZ//MP2/6-31+G(d) | 48.6 | ″ |
MP2/6-311++G(d,p) | 51.3 | Nguyen 1997 (13); Alavi 2002 (15) |
MP2/6-311++G(d,p) + CPc,d | 46.1 | Dmitrova 2000 (14) |
ωB97X-V/def2-TZVPD | 50.8 | Present work |
ωB97X-D3/def2-TZVPD | 51.9 | ″ |
B3LYP-D3/6-311++G(d,p)d | 58.6 | Ling 2019 (22) |
B3LYP/6-311++G(d,p)d | 51.8 | Alavi 2002 (15) |
M06-2X/def2-TZVPD | 55.1 | Present work |
MN12-SX/def2-TZVPD | 48.2 | ″ |
ωB97X-D3/def2-TZVPD//ωB97X-D3/def2-SVPD | 52.3 | ″ |
D0 is the zero-temperature dissociation energy in kJ/mol. Unless otherwise indicated, all zero-point energy corrections used unscaled harmonic frequencies obtained at the optimization level.
Includes an anharmonic zero-point energy correction at the MP2/aug-cc-pVTZ level of theory as well as a torsion-corrected partition function.
Includes a counterpoise correction to the energy for basis set superposition error (BSSE).
Calculations presented originally did not include a zero-point energy correction, but this has been implemented in the present work.
Figure 2
Figure 2. [(NH4)2NO3]+ (upper) and (lower) structures optimized at the ωB97X-D3/def2-SVPD level of theory and those reported by Dunlap and Doyle (23) using the BP functional (right). Adapted from 23. Copyright 1996 American Chemical Society.
Cation | Anion | Neutral | ||||
---|---|---|---|---|---|---|
Model chemistry | –Ve | RMSD | –Ve | RMSD | –Ve | RMSD |
Au-CCSD(T) //MP2/aug-cc-pVTZb | 163.5 | 164.0 | 280.3 | |||
MP2/CBS//MP2/aug-cc-pVTZb | 163.5 | 163.6 | 280.6 | |||
MP2/aug-cc-pVTZ | 165.2 | 164.8 | 283.5 | |||
ωB97M-V/def2-TZVPD | 164.4 | 0.8% | 163.9 | 1.8% | 280.1 | 1.5% |
ωB97X-D3/def2-TZVPD | 164.8 | 0.8% | 164.0 | 0.8% | 280.2 | 0.9% |
M06-2X/def2-TZVPD | 165.2 | 1.7% | 164.7 | 0.3% | 281.3 | 1.7% |
MN12-SX/def2-TZVPD | 162.8 | 0.7% | 162.5 | 1.5% | 277.2 | 3.4% |
B3LYP-D3/6-311++G(d,p) | 165.3 | 1.6% | 165.2 | 2.3% | 281.8 | 2.0% |
ωB97X-D3/def2- TZVPD // ωB97X-D3/def2- SVPD | 164.8 | 0.3% | 163.9 | 0.9% | 280.2 | 0.6% |
Ve is the interaction energy in kcal/mol; RMSD is the root-mean-squared percent deviations of nearest-neighbor distances from MP2/aug-cc-pVTZ values.
The Au-CCSD(T) and MP2/CBS calculations are described in the Methods section.
Results
Figure 3
Figure 3. Positive-ion sputtered mass spectrum of ammonium nitrate clusters. (23) Predicted ωB97X-D3 structures of parent and daughter ions corresponding to the numbered peaks have been added to the original spectrum. Adapted from 23. Copyright 1996 American Chemical Society.
Figure 4
Figure 4. ωB97X-D3 electronic binding energies for different fragmentation channels of .
Figure 5
Figure 5. ωB97X-D3 and OPLS/TR differential interaction energies for the parents.
Figure 6
Figure 6. Negative-ion sputtered mass spectrum of ammonium nitrate clusters. (23) Predicted structures of parent ions corresponding to the numbered peaks have been added to the original spectrum. Adapted from 23. Copyright 1996 American Chemical Society.
Figure 7
Figure 7. ωB97X-D3 electronic binding energies for different fragmentation channels of cations.
Figure 8
Figure 9
Figure 9. ωB97X-D3 (DFT) and OPLS/TR differential interaction energies for the parents.
Figure 10
Figure 10. Predicted structures of selected (NH4NO3)n nanoparticles from OPLS/TR calculations followed by ωB97X-D3/def2-SVPD geometry optimization.
Figure 11
Figure 11. ωB97X-D3 differential interaction energies for (NH4NO3)n from OPLS-AA (black) and ωB97X-D3/def2-TZPD calculations (blue). Also shown: ωB97X-D3 calculations using a 6-311+G(2df,2p)[6-311G(d)] “Pople” basis; see text (orange). The optimized n = 4, 6, 9, 16, 21, 27, and 37 structures are shown.
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.4c04630.
Detailed description of optimization parameters. OPLS-AA parameters used in the simulated annealing calculations are provided. Computed interaction energies of (neutral) nanoparticles and cation and anion clusters. The computed energies of all species presented in this work. The coordinates in XYZ format for all ωB97X-D3/def2-SVPD optimized cation and anion clusters and nanoparticles. The optimized OPLS-AA and ωB97X-D3/6-31G(d) structures in XYZ format for the nanoparticles presented in this work (PDF)
Structures of ammonium nitrate(ZIP)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
The molecular images in this article were created with the help of the Avogadro and Spartan 24 software packages. (62,63) We are grateful to Steven L. Topper for his continued development and improvement of TransRot. (64) We thank Abdullah S. Hassan and Sangjoon Lee for their advice and assistance, and Anna J.V. Lomboy for helpful conversations regarding ammonium nitrate nanoparticles. This work was not supported by external funding sources.
References
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- 5Chee, S.; Barsanti, K.; Smith, J. N.; Myllys, N. A Predictive Model for Salt Nanoparticle Formation Using Heterodimer Stability Calculations. Atmos. Chem. Phys. 2021, 21, 11637– 11654, DOI: 10.5194/acp-21-11637-2021Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvFWhtbzE&md5=79bc95e833ac430a15012709829250faA predictive model for salt nanoparticle formation using heterodimer stability calculationsChee, Sabrina; Barsanti, Kelley; Smith, James N.; Myllys, NannaAtmospheric Chemistry and Physics (2021), 21 (15), 11637-11654CODEN: ACPTCE; ISSN:1680-7324. (Copernicus Publications)The best predictor of heterodimer stability was found to be gas-phase acidity. We then analyzed the relationship between heterodimer stability and J4 x 4, the theor. predicted formation rate of a four-acid, four-base cluster, for sulfuric acid salts over a range of monomer concns. from 105 to 109 molec cm-3 and temps. from 248 to 348 K and found that heterodimer stability forms a lognormal relationship with J4 x 4. However, temp. and concn. effects made it difficult to form a predictive expression of J4 x 4. In order to reduce those effects, heterodimer concn. was calcd. from heterodimer stability and yielded an expression for predicting J4 x 4 for any salt, given approx. equal acid and base monomer concns. and knowledge of monomer concn. and temp. This parameterization was tested for the sulfuric acid-ammonia system by comparing the predicted values to exptl. data and was found to be accurate within 2 orders of magnitude. We show that one can create a simple parameterization that incorporates the dependence on temp. and monomer concn. on J4 x 4 by defining a new term that we call the normalized heterodimer concn., Φ. A plot of J4 x 4 vs. Φ collapses to a single monotonic curve for weak sulfate salts (difference in gas-phase acidity >95 kcal mol-1) and can be used to accurately est. J4 x 4 within 2 orders of magnitude in atm. models.
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- 14Dimitrova, Y.; Peyerimhoff, S. D. Ab Initio Study of Structures of Hydrogen-bonded Nitric Acid Complexes. Chem. Phys. 2000, 254, 125– 134, DOI: 10.1016/S0301-0104(00)00024-0Google ScholarThere is no corresponding record for this reference.
- 15Alavi, S.; Thompson, D. L. Theoretical Study of Proton Transfer in Ammonium Nitrate Clusters. J. Chem. Phys. 2002, 117 (6), 2599– 2608, DOI: 10.1063/1.1489995Google ScholarThere is no corresponding record for this reference.
- 16Chien, W.-M.; Chandra, D.; Lau, K. H.; Hildenbrand, D. L.; Helmy, A. M. The Vaporization of NH4NO3. J. Chem. Thermodyn. 2010, 42, 846– 651, DOI: 10.1016/j.jct.2010.01.012Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXlsVGjtL4%253D&md5=d77abcc966f9e3163d0e00e8f534b1c7The vaporization of NH4NO3Chien, Wen-Ming; Chandra, Dhanesh; Lau, K.-H.; Hildenbrand, D. L.; Helmy, A. M.Journal of Chemical Thermodynamics (2010), 42 (7), 846-851CODEN: JCTDAF; ISSN:0021-9614. (Elsevier Ltd.)The total vapor pressure and vapor mol. wt. of ammonium nitrate (NH4NO3) were detd. The vapor pressure was detd. by the torsion + effusion method, and vapor compn. was detd. by effusion-beam mass spectrometry. Total vapor pressures of NH4NO3 were measured by using two effusion cells with different orifice diams. over the pressure range of 10-6 to 10-3 kPa between 313 and 360 K. The equil. vapor pressure equation was zero-extrapolated from measurements with different orifice Knudsen cells, P1 and P2 cells, and is given as: log PT (kPa) = (10.400 ± 0.0002) - (4783.16 ± 0.07)/T. The measured mol. wt. of NH4NO3 is 48.7 g/mol for P1 cell and 50.7 g/mol for P2 cell, both of which are much less than the theor. mol. wt. of NH4NO3 (approx. 80.04 g/mol). This significant difference in mol. wt. suggests that there is disproportionation of NH4NO3 samples. The mass spectroscopic results revealed that NH4NO3 decomps. to NH3 and HNO3; it was interesting to note that the expected N2, O2, and H2O gases were not evolved during vaporization. The partial pressures of the three gas phase species (NH4NO3, NH3, and HNO3) that were evolved during vaporization of NH4NO3 sample were detd. as: P1 cell: PNH4NO3/PT = 0.1490, PNH3/PT = 0.2911, and PHNO3/PT = 0.5599, and P2 cell: PNH4NO3/PT = 0.2101, PNH3/PT = 0.2702, and PHNO3/PT = 0.5197. The std. Gibbs energy change (ΔG°) for NH4NO3 decompn. and sublimation reactions are obtained from the partial pressure results. Details of total and partial pressures of vaporization of NH4NO3 and disproportionation aspects of the evolved gases are presented.
- 17Hildenbrand, D. L.; Lau, K. H.; Chandra, D. Thermochemistry of Gaseous Ammonium Nitrate, NH4NO3 (g). J. Chem. Phys. A 2010, 114, 111654– 111655, DOI: 10.1021/jp105773qGoogle ScholarThere is no corresponding record for this reference.
- 18Irikura, K. K. Thermochemistry of Ammonium Nitrate, NH4NO3, in the Gas Phase. J. Phys. Chem. A 2010, 114, 11651– 11653, DOI: 10.1021/jp105770dGoogle Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXht1KhsLbL&md5=78893cfed35759afefd7a7b3a160b1b5Thermochemistry of Ammonium Nitrate, NH4NO3, in the Gas PhaseIrikura, Karl K.Journal of Physical Chemistry A (2010), 114 (43), 11651-11653CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)Hildenbrand and co-workers have shown recently that the vapor above solid ammonium nitrate includes mols. of NH4NO3, not only NH3 and HNO3 as previously believed. Their measurements led to thermochem. values that imply an enthalpy change of D298 = 98 ± 9 kJ mol-1 for the gas-phase dissocn. of ammonium nitrate into NH3 and HNO3. Using updated spectroscopic information for the partition function leads to the revised value of D298 = 78 ± 21 kJ mol-1 (accompanying paper in this journal, Hildenbrand, D. L.; Lau, K. H.; Chandra, D. J. Phys. Chem. B2010, DOI: 10.1021/jp105773q00080533A). In contrast, high-level ab initio calcns., detailed in the present report, predict a dissocn. enthalpy half as large as the original result, 50 ± 3 kJ mol-1. These are frozen-core CCSD(T) calcns. extrapolated to the limiting basis set aug-cc-pV∞Z using an anharmonic vibrational partition function and a variational treatment of the NH3 rotor. The corresponding enthalpy of formation is ΔfH298°(NH4NO3,g) = -230.6 ± 3 kJ mol-1. The origin of the disagreement with expt. remains unexplained.
- 19Marechal, Y. The Hydrogen Bond and the Water Molecule; Elsevier: Amsterdam, 2007.Google ScholarThere is no corresponding record for this reference.
- 20Takeuchi, J.; Masuda, Y.; Clark, R.; Takeda, K. Theoretical Studies on Proton Transfer in Ammonium Nitrate Monomer and Dimer. Japanese J. Appl. Phys. 2013, 52 (7R), 076302, DOI: 10.7567/JJAP.52.076302Google ScholarThere is no corresponding record for this reference.
- 21Cagnina, S.; Rotureau, P.; Fayet, G.; Adamo, C. The Ammonium Nitrate and Its Mechanism of Decomposition in the Gas Phase: A Theoretical Study and a DFT Benchmark. Phys. Chem. Chem. Phys. 2013, 15, 10849– 10858, DOI: 10.1039/c3cp50368bGoogle Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXptFCntLw%253D&md5=f349b1d73474bc6601969020e71a9cf7The ammonium nitrate and its mechanism of decomposition in the gas phase: a theoretical study and a DFT benchmarkCagnina, Stefania; Rotureau, Patricia; Fayet, Guillaume; Adamo, CarloPhysical Chemistry Chemical Physics (2013), 15 (26), 10849-10858CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)The decompn. mechanism of ammonium nitrate in the gas phase was investigated and fully characterized by means of CBS-QB3 calcns. Five reaction channels were identified, leading to the formation of products (N2, H2O, O2, OH, HNO, NO3) found in the exptl. works. The identified mechanism well underlines the origin of the chem. hazard of ammonium nitrate which is related to the exothermicity of the lowest decompn. channels. Furthermore, the high barrier to overcome in the rate detg. step well explained the fact that the reaction is not usually spontaneous and requires a significant external stimulus for its onset. An accurate DFT benchmark study was then conducted to det. the most suitable exchange-correlation functional to accurately describe the reaction profile both in terms of structures and thermochem. This evaluation supports the use of the M06-2X functional as the best option for the study of ammonium nitrate decompn. and related reactions. Indeed, this level of theory provided the lowest deviations with respect to CBS-QB3 ref. values, outperforming functionals esp. developed for reaction kinetics.
- 22Ling, J.; Ding, X.; Li, Z.; Yang, J. First-Principles Study of Molecular Clusters Formed by Nitric Acid and Ammonia. J. Phys. Chem. A 2019, 121, 661– 668, DOI: 10.1021/acs.jpca.6b09185Google ScholarThere is no corresponding record for this reference.
- 23Dunlap, B. I.; Doyle, R. J. J. Ammonium Nitrate Cluster Ions. J. Phys. Chem. 1996, 100, 5281– 5285, DOI: 10.1021/jp9516755Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XhsVGgtLc%253D&md5=4b85e764db960a5356167638022e716cAmmonium Nitrate Cluster IonsDunlap, Brett I.; Doyle, Robert J., Jr.Journal of Physical Chemistry (1996), 100 (13), 5281-5CODEN: JPCHAX; ISSN:0022-3654. (American Chemical Society)Sputtering of condensed-phase ammonium nitrate yields many pos. and neg. cluster ion series derived from different ionic cores. The cluster cores are surrounded by varying nos. of ammonium nitrate monomer units. Most interesting is the extensive series of neg. cluster ions of the form [(NH4NO3)nNO3]-, n ≥ 3. The corresponding pos. clusters, [(NH4NO3)nNH4]+, are also very extensive but also include the smallest ions, n = 1 and 2. Collision-induced dissocn. of mass-selected cluster ions suggests that the first two members of the neg. series, n = 1 and n = 2, are not detected because they rearrange and lose one or more ammonia mols. Gradient-d.-functional calcns. using two different functionals predict that NH4NO3 is strongly hydrogen bonded and that [(NH4NO3)NO3]- has no hydrogen bonds. This is consistent with this ion rearranging by loss of NH3 to form the strongly hydrogen-bonded ion [H(NO3)2]-. Rearrangements involving loss of ammonia mols. in the neg.-ion spectrum and nitric acid mols. in the pos.-ion spectrum lead to a rich variety of other, less extensive, series of sputtered ions from this complex solid. Both relative gradient-d.-functional energies correlate well with whether or not various ions are observable exptl.
- 24Lin, Y.; Li, G.; Mao, S.; Chai, J. Long-range Corrected Hybrid Density Functionals With Improved Dispersion Corrections. J. Chem. Theory Comput. 2013, 9, 263– 272, DOI: 10.1021/ct300715sGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xhs1WltLrP&md5=8b6cf43f9d58e66754405fb28fd70438Long-Range Corrected Hybrid Density Functionals with Improved Dispersion CorrectionsLin, You-Sheng; Li, Guan-De; Mao, Shan-Ping; Chai, Jeng-DaJournal of Chemical Theory and Computation (2013), 9 (1), 263-272CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)By incorporating the improved empirical atom-atom dispersion corrections from DFT-D3 [Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys.2010, 132, 154104], two long-range cor. (LC) hybrid d. functionals are proposed. Our resulting LC hybrid functionals, ωM06-D3 and ωB97X-D3, are shown to be accurate for a very wide range of applications, such as thermochem., kinetics, noncovalent interactions, frontier orbital energies, fundamental gaps, and long-range charge-transfer excitations, when compared with common global and LC hybrid functionals. Relative to ωB97X-D [Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys.2008, 10, 6615], ωB97X-D3 (reoptimization of ωB97X-D with improved dispersion corrections) is shown to be superior for nonbonded interactions, and similar in performance for bonded interactions, while ωM06-D3 is shown to be superior for general applications.
- 25Topper, R. Q.; Topper, S. L.; Lee, S. TransRot: A Portable Software Package for Simulated Annealing Monte Carlo Geometry Optimization of Atomic and Molecular Clusters. In ACS Symposium Series, Parish, C.A.; Hopkins, T.A., Eds.; ACS Publications: Washington DC, 2022; Vol. 1428; pp. 19 38. DOI: 10.1021/bk-2022-1428.ch002 .Google ScholarThere is no corresponding record for this reference.
- 26Jorgensen, W. L.; Maxwell, D. S.; Tirado-Rives, J. Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids. J. Am. Chem. Soc. 1996, 118, 11225– 11236, DOI: 10.1021/ja9621760Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XmtlOitrs%253D&md5=fef2924a69421881390282aa309ae91bDevelopment and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic LiquidsJorgensen, William L.; Maxwell, David S.; Tirado-Rives, JulianJournal of the American Chemical Society (1996), 118 (45), 11225-11236CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The parametrization and testing of the OPLS all-atom force field for org. mols. and peptides are described. Parameters for both torsional and nonbonded energetics have been derived, while the bond stretching and angle bending parameters have been adopted mostly from the AMBER all-atom force field. The torsional parameters were detd. by fitting to rotational energy profiles obtained from ab initio MO calcns. at the RHF/6-31G*//RHF/6-31G* level for more than 50 org. mols. and ions. The quality of the fits was high with av. errors for conformational energies of less than 0.2 kcal/mol. The force-field results for mol. structures are also demonstrated to closely match the ab initio predictions. The nonbonded parameters were developed in conjunction with Monte Carlo statistical mechanics simulations by computing thermodn. and structural properties for 34 pure org. liqs. including alkanes, alkenes, alcs., ethers, acetals, thiols, sulfides, disulfides, aldehydes, ketones, and amides. Av. errors in comparison with exptl. data are 2% for heats of vaporization and densities. The Monte Carlo simulations included sampling all internal and intermol. degrees of freedom. It is found that such non-polar and monofunctional systems do not show significant condensed-phase effects on internal energies in going from the gas phase to the pure liqs.
- 27Jorgensen, W. L.; Tirado-Rives, J. Molecular Modeling of Organic and Biomolecular Systems Using BOSS and MCPRO. J. Comput. Chem. 2005, 26, 1689– 1700, DOI: 10.1002/jcc.20297Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXht1SlsbbN&md5=e487e9838d39e4b39a5d06a240bfc1e0Molecular modeling of organic and biomolecular systems using BOSS and MCPROJorgensen, William L.; Tirado-Rives, JulianJournal of Computational Chemistry (2005), 26 (16), 1689-1700CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)An overview is provided of the capabilities for the current versions of the BOSS and MCPRO programs for mol. modeling of org. and biomol. systems. Recent applications are noted, particularly for QM/MM studies of org. and enzymic reactions and for protein-ligand binding.
- 28Tinker version 8.11; Washington University in St. Louis: St: Louis, MO, USA, 2024. https://dasher.wustl.edu/tinker/. accessed August 28, 2024.Google ScholarThere is no corresponding record for this reference.
- 29Topper, R. Q.; Freeman, D. L.; Bergin, D.; LaMarche, K. Computational Techniques and Strategies for Monte Carlo Thermodynamic Calculations With Applications to Nanoclusters. In Reviews in Computational Chemistry ISBN 0–471–23585–7, Lipkowitz, K. B.; Larter, R.; Cundari, T.R., Eds.; Wiley-VCH/John Wiley and Sons: New York, 2003; Vol. 19, pp. 1 41.Google ScholarThere is no corresponding record for this reference.
- 30Torres, F. M.; Agichtein, E.; Grinberg, L.; Yu, G.; Topper, R. Q. A Note on the Application of the “Boltzmann Simplex”-Simulated Annealing Algorithm to Global Optimizations of Argon and Water Clusters. J. Mol. Struct. (THEOCHEM) 1997, 419, 85– 95, DOI: 10.1016/S0166-1280(97)00195-4Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXmvFCkug%253D%253D&md5=d31fd6733a352aa82b87bdc30a9c2faaA note on the application of the "Boltzmann simplex"-simulated annealing algorithm to global optimizations of argon and water clustersTorres, Francis M.; Agichtein, Eugene; Grinberg, Leonid; Yu, Guowei; Topper, Robert Q.Journal of Molecular Structure: THEOCHEM (1997), 419 (), 85-95CODEN: THEODJ; ISSN:0166-1280. (Elsevier Science B.V.)We report our application of a recently published simulated annealing algorithm which we call "Boltzmann simplex"-simulated annealing (BSSA) to global optimizations of argon and water clusters. The Lennard-Jones model of argon clusters serves as a challenging benchmark for global optimization methods, and we use it as a test case. The BSSA method is most useful when followed by a local optimization via the Powell method. This is because the Powell method quenches to the equil. geometry more effectively than a downhill simplex, which is the zero-temp. limit of the BSSA algorithm. We also find that very slow annealing rates are required to achieve acceptable results. A study of small water clusters [(H2O)m, m = 2-6] using a recently published flexible-monomer interaction potential yields ring-like structures which are in good agreement with other theor. and exptl. studies for m = 3-5. A highly puckered ring structure is obtained for m = 6.
- 31Digges, T. G.; Rosenberg, S. J.; Geil, G. W. Heat Treatment And Properties Of Iron And Steel, National Bureau of Standards Monograph 88, 1966, https://nvlpubs.nist.gov/nistpubs/legacy/mono/nbsmonograph88.pdf.Google ScholarThere is no corresponding record for this reference.
- 32Leary, R. H. Global Optimization on Funneling Landscapes. J. Global Optim. 2000, 18, 367– 383, DOI: 10.1023/A:1026500301312Google ScholarThere is no corresponding record for this reference.
- 33Locatelli, M.; Schoen, F. Efficient Algorithms for Large Scale Global Optimization: Lennard-Jones Clusters. Comput. Optim. Appl. 2003, 26, 173– 190, DOI: 10.1023/A:1025798414605Google ScholarThere is no corresponding record for this reference.
- 34Wales, D. J.; Doye, J. P. K. Global Optimization by Basin-Hopping and the Lowest Energy Structures of Lennard-Jones Clusters Containing Up to 110 Atoms. J. Phys. Chem. A 1997, 101, 5111– 5116, DOI: 10.1021/jp970984nGoogle Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXktVGrurY%253D&md5=f40693ff24b5c84a8c482fa18ec1eb47Global Optimization by Basin-Hopping and the Lowest Energy Structures of Lennard-Jones Clusters Containing up to 110 AtomsWales, David J.; Doye, Jonathan P. K.Journal of Physical Chemistry A (1997), 101 (28), 5111-5116CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)We describe a global optimization technique using "basin-hopping" in which the potential energy surface is transformed into a collection of interpenetrating staircases. This method has been designed to exploit the features that recent work suggests must be present in an energy landscape for efficient relaxation to the global min. The transformation assocs. any point in configuration space with the local min. obtained by a geometry optimization started from that point, effectively removing transition state regions from the problem. However, unlike other methods based upon hypersurface deformation, this transformation does not change the global min. The lowest known structures are located for all Lennard-Jones clusters up to 110 atoms, including a no. that have never been found before in unbiased searches.
- 35González, B. S.; Noya, E. G.; Vega, C.; Sesé, L. M. Nuclear Quantum Effects in Water Clusters: The Role of the Molecular Flexibility. J. Phys. Chem. B 2010, 114, 2484– 2492, DOI: 10.1021/jp910770yGoogle Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtlCgt7w%253D&md5=acd19d381a4c4e6d367bea544e43ee97Nuclear Quantum Effects in Water Clusters: The Role of the Molecular FlexibilityGonzalez, Briesta S.; Noya, Eva G.; Vega, Carlos; Sese, Luis M.Journal of Physical Chemistry B (2010), 114 (7), 2484-2492CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)With the objective of establishing the importance of water flexibility in empirical models which explicitly include nuclear quantum effects, we have carried out path integral Monte Carlo simulations in water clusters with up to seven mols. Two recently developed models have been used for comparison: the rigid TIP4PQ/2005 and the flexible q-TIP4P/F models, both inspired by the rigid TIP4P/2005 model. To obtain a starting configuration for our simulations, we have located the global min. for the rigid TIP4P/2005 and TIP4PQ/2005 models and for the flexible q-TIP4P/F model. All the structures are similar to those predicted by the rigid TIP4P potential showing that the charge distribution mainly dets. the global min. structure. For the flexible q-TIP4P/F model, we have studied the geometrical distortion upon isotopic substitution by studying tritiated water clusters. Our results show that tritiated water clusters exhibit an rOT distance shorter than the rOH distance in water clusters, not significant changes in the ΦHOH angle, and a lower av. dipole moment than water clusters. We have also carried out classical simulations with the rigid TIP4PQ/2005 model showing that the rotational kinetic energy is greatly affected by quantum effects, but the translational kinetic energy is only slightly modified. The potential energy is also noticeably higher than in classical simulations. Finally, as a concluding remark, we have calcd. the formation energies of water clusters using both models, finding that the formation energies predicted by the rigid TIP4PQ/2005 model are lower by roughly 0.6 kcal/mol than those of the flexible q-TIP4P/F model for clusters of moderate size, the origin of this difference coming mainly from the geometrical distortion of the water mol. in the clusters that causes an increase in the intramol. potential energy.
- 36stlaPblog: a blog about Mathematics, R, Statistics. Rotation in Spherical Coordinates , 2016 https://stla.github.io/stlapblog/posts/RotationSphericalCoordinates.html. accessed 2024 April 29.Google ScholarThere is no corresponding record for this reference.
- 37Miller Iii, T. F.; Eleftheriou, M.; Pattnaik, P.; Ndirango, A.; Newns, D.; Martyna, G. J. Symplectic Quaternion Scheme for Biophysical Molecular Dynamics. J. Chem. Phys. 2002, 116 (20), 8649– 8659, DOI: 10.1063/1.1473654Google ScholarThere is no corresponding record for this reference.
- 38Weigend, F.; Ahlrichs, R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297– 3305, DOI: 10.1039/b508541aGoogle Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXpsFWgu7o%253D&md5=a820fb6055c993b50c405ba0fc62b194Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracyWeigend, Florian; Ahlrichs, ReinhartPhysical Chemistry Chemical Physics (2005), 7 (18), 3297-3305CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 mols. representing (nearly) all elements-except lanthanides-in their common oxidn. states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, d. functional theory and correlated methods, for which we had chosen Moller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.
- 39Bursch, M.; Mewes, J.-M.; Hansen, A.; Grimme, S. Best-practice DFT Protocols for Basic Molecular Computational Chemistry. Angew. Chem., Int. Ed. 2022, 61, e202205735 DOI: 10.1002/anie.202205735Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xitl2kt7%252FO&md5=c562b2bd16bea8edc1ae18ad65216ce2Best-Practice DFT Protocols for Basic Molecular Computational ChemistryBursch, Markus; Mewes, Jan-Michael; Hansen, Andreas; Grimme, StefanAngewandte Chemie, International Edition (2022), 61 (42), e202205735CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Nowadays, many chem. investigations are supported by routine calcns. of mol. structures, reaction energies, barrier heights, and spectroscopic properties. The lion's share of these quantum-chem. calcns. applies d. functional theory (DFT) evaluated in at.-orbital basis sets. This work provides best-practice guidance on the numerous methodol. and tech. aspects of DFT calcns. in three parts: Firstly, we set the stage and introduce a step-by-step decision tree to choose a computational protocol that models the expt. as closely as possible. Secondly, we present a recommendation matrix to guide the choice of functional and basis set depending on the task at hand. A particular focus is on achieving an optimal balance between accuracy, robustness, and efficiency through multi-level approaches. Finally, we discuss selected representative examples to illustrate the recommended protocols and the effect of methodol. choices.
- 40Mardirossian, N.; Head-Gordon, M. ωB97M-V: A Combinatorially Optimized, Range-Separated Hybrid, Meta-GGA Density Functional with VV10 Nonlocal Correlation. J. Chem. Phys. 2016, 144, 214110, DOI: 10.1063/1.4952647Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XpsF2lt78%253D&md5=785288128d893d3914f3326f374b96d4ωB97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlationMardirossian, Narbe; Head-Gordon, MartinJournal of Chemical Physics (2016), 144 (21), 214110/1-214110/23CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A combinatorially optimized, range-sepd. hybrid, meta-GGA d. functional with VV10 nonlocal correlation is presented. The final 12-parameter functional form is selected from approx. 10 × 109 candidate fits that are trained on a training set of 870 data points and tested on a primary test set of 2964 data points. The resulting d. functional, ωB97M-V, is further tested for transferability on a secondary test set of 1152 data points. For comparison, ωB97M-V is benchmarked against 11 leading d. functionals including M06-2X, ωB97X-D, M08-HX, M11, ωM05-D, ωB97X-V, and MN15. Encouragingly, the overall performance of ωB97M-V on nearly 5000 data points clearly surpasses that of all of the tested d. functionals. In order to facilitate the use of ωB97M-V, its basis set dependence and integration grid sensitivity are thoroughly assessed, and recommendations that take into account both efficiency and accuracy are provided. (c) 2016 American Institute of Physics.
- 41Zhao, Y.; Truhlar, D. G. The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Functionals. Theor. Chem. Acc. 2008, 120, 215– 241, DOI: 10.1007/s00214-007-0310-xGoogle Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXltFyltbY%253D&md5=c31d6f319d7c7a45aa9b716220e4a422The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionalsZhao, Yan; Truhlar, Donald G.Theoretical Chemistry Accounts (2008), 120 (1-3), 215-241CODEN: TCACFW; ISSN:1432-881X. (Springer GmbH)We present two new hybrid meta exchange-correlation functionals, called M06 and M06-2X. The M06 functional is parametrized including both transition metals and nonmetals, whereas the M06-2X functional is a high-nonlocality functional with double the amt. of nonlocal exchange (2X), and it is parametrized only for nonmetals. The functionals, along with the previously published M06-L local functional and the M06-HF full-Hartree-Fock functionals, constitute the M06 suite of complementary functionals. We assess these four functionals by comparing their performance to that of 12 other functionals and Hartree-Fock theory for 403 energetic data in 29 diverse databases, including ten databases for thermochem., four databases for kinetics, eight databases for noncovalent interactions, three databases for transition metal bonding, one database for metal atom excitation energies, and three databases for mol. excitation energies. We also illustrate the performance of these 17 methods for three databases contg. 40 bond lengths and for databases contg. 38 vibrational frequencies and 15 vibrational zero point energies. We recommend the M06-2X functional for applications involving main-group thermochem., kinetics, noncovalent interactions, and electronic excitation energies to valence and Rydberg states. We recommend the M06 functional for application in organometallic and inorganometallic chem. and for noncovalent interactions.
- 42Peverati, R.; Truhlar, D. G. Screened-Exchange Density Functionals With Broad Accuracy for Chemistry and Solid-State Physics. Phys. Chem. Chem. Phys. 2012, 14, 16187– 16191, DOI: 10.1039/c2cp42576aGoogle Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xhs12jurbM&md5=c718c8b5a8e7aa2fc831216439b9ea31Screened-exchange density functionals with broad accuracy for chemistry and solid-state physicsPeverati, Roberto; Truhlar, Donald G.Physical Chemistry Chemical Physics (2012), 14 (47), 16187-16191CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)We present two new exchange-correlation functionals for hybrid Kohn-Sham electronic structure calcns. based on the nonseparable functional form introduced recently in the N12 and MN12-L functionals but now with the addn. of screened Hartree-Fock exchange. The 1st functional depends on the d. and the d. gradient and is called N12-SX; the 2nd functional depends on the d., the d. gradient, and the kinetic energy d. and is called MN12-SX. Both new functionals include a portion of the Hartree-Fock exchange at short-range, but Hartree-Fock exchange is screened at long range. The accuracies of the 2 new functionals are compared to those of the recent N12 and MN12-L local functionals to show the effect of adding screened exchange, are compared to the previously best available screened exchange functional, HSE06, and are compared to the best available global-hybrid generalized gradient approxn. (GGA) and to a high-performance long-range-cor. meta-GGA.
- 43Grimme, S.; Antony, J.; Ehrlich, S.; Krief, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132 (15), 154104, DOI: 10.1063/1.3382344Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXkvVyks7o%253D&md5=2bca89d904579d5565537a0820dc2ae8A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-PuGrimme, Stefan; Antony, Jens; Ehrlich, Stephan; Krieg, HelgeJournal of Chemical Physics (2010), 132 (15), 154104/1-154104/19CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The method of dispersion correction as an add-on to std. Kohn-Sham d. functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coeffs. and cutoff radii that are both computed from first principles. The coeffs. for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination nos. (CN). They are used to interpolate between dispersion coeffs. of atoms in different chem. environments. The method only requires adjustment of two global parameters for each d. functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of at. forces. Three-body nonadditivity terms are considered. The method has been assessed on std. benchmark sets for inter- and intramol. noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean abs. deviations for the S22 benchmark set of noncovalent interactions for 11 std. d. functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C6 coeffs. also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in mols. and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems. (c) 2010 American Institute of Physics.
- 44Mardirossian, N.; Head-Gordon, M. Thirty Years of Density Functional Theory in Computational Chemistry: an Overview and Extensive Assessment of 200 Density Functionals. Mol. Phys. 2017, 115 (19), 2315– 2372, DOI: 10.1080/00268976.2017.1333644Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVCltb3O&md5=ba27d707ee3f5fcdd949644d3d2cbd5eThirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionalsMardirossian, Narbe; Head-Gordon, MartinMolecular Physics (2017), 115 (19), 2315-2372CODEN: MOPHAM; ISSN:0026-8976. (Taylor & Francis Ltd.)In the past 30 years, Kohn-Sham d. functional theory has emerged as the most popular electronic structure method in computational chem. To assess the ever-increasing no. of approx. exchange-correlation functionals, this review benchmarks a total of 200 d. functionals on a mol. database (MGCDB84) of nearly 5000 data points. The database employed, provided as Supplemental Data, is comprised of 84 data-sets and contains non-covalent interactions, isomerisation energies, thermochem., and barrier heights. In addn., the evolution of non-empirical and semi-empirical d. functional design is reviewed, and guidelines are provided for the proper and effective use of d. functionals. The most promising functional considered is ωB97M-V, a range-sepd. hybrid meta-GGA with VV10 nonlocal correlation, designed using a combinatorial approach. From the local GGAs, B97-D3, revPBE-D3, and BLYP-D3 are recommended, while from the local meta-GGAs, B97M-rV is the leading choice, followed by MS1-D3 and M06-L-D3. The best hybrid GGAs are ωB97X-V, ωB97X-D3, and ωB97X-D, while useful hybrid meta-GGAs (besides ωB97M-V) include ωM05-D, M06-2X-D3, and MN15. Ultimately, today's state-of-the-art functionals are close to achieving the level of accuracy desired for a broad range of chem. applications, and the principal remaining limitations are assocd. with systems that exhibit significant self-interaction/delocalisation errors and/or strong correlation effects.
- 45Neese, F.; Wennmohs, F.; Becker, U.; Riplinger, C. The ORCA Quantum Chemistry Package. J. Chem. Phys. 2020, 152, 224– 108, DOI: 10.1063/5.0004608Google ScholarThere is no corresponding record for this reference.
- 46Epifanovsky, E.; Gilbert, A. T. B.; Feng, X.; Lee, J.; Mao, Y.; Mardirossian, N.; Pokhilko, P.; White, A. F.; Coons, M. P.; Dempwolff, A. L.; Gan, Z. Software for the Frontiers of Quantum Chemistry: An Overview of Developments in the Q-Chem 5 package. J. Chem. Phys. 2021, 155 (8), 084801, DOI: 10.1063/5.0055522Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvVymsb3P&md5=34fdc0f501633082f75521c06be38ab2Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 packageEpifanovsky, Evgeny; Gilbert, Andrew T. B.; Feng, Xintian; Lee, Joonho; Mao, Yuezhi; Mardirossian, Narbe; Pokhilko, Pavel; White, Alec F.; Coons, Marc P.; Dempwolff, Adrian L.; Gan, Zhengting; Hait, Diptarka; Horn, Paul R.; Jacobson, Leif D.; Kaliman, Ilya; Kussmann, Jorg; Lange, Adrian W.; Lao, Ka Un; Levine, Daniel S.; Liu, Jie; McKenzie, Simon C.; Morrison, Adrian F.; Nanda, Kaushik D.; Plasser, Felix; Rehn, Dirk R.; Vidal, Marta L.; You, Zhi-Qiang; Zhu, Ying; Alam, Bushra; Albrecht, Benjamin J.; Aldossary, Abdulrahman; Alguire, Ethan; Andersen, Josefine H.; Athavale, Vishikh; Barton, Dennis; Begam, Khadiza; Behn, Andrew; Bellonzi, Nicole; Bernard, Yves A.; Berquist, Eric J.; Burton, Hugh G. A.; Carreras, Abel; Carter-Fenk, Kevin; Chakraborty, Romit; Chien, Alan D.; Closser, Kristina D.; Cofer-Shabica, Vale; Dasgupta, Saswata; de Wergifosse, Marc; Deng, Jia; Diedenhofen, Michael; Do, Hainam; Ehlert, Sebastian; Fang, Po-Tung; Fatehi, Shervin; Feng, Qingguo; Friedhoff, Triet; Gayvert, James; Ge, Qinghui; Gidofalvi, Gergely; Goldey, Matthew; Gomes, Joe; Gonzalez-Espinoza, Cristina E.; Gulania, Sahil; Gunina, Anastasia O.; Hanson-Heine, Magnus W. D.; Harbach, Phillip H. P.; Hauser, Andreas; Herbst, Michael F.; Hernandez Vera, Mario; Hodecker, Manuel; Holden, Zachary C.; Houck, Shannon; Huang, Xunkun; Hui, Kerwin; Huynh, Bang C.; Ivanov, Maxim; Jasz, Adam; Ji, Hyunjun; Jiang, Hanjie; Kaduk, Benjamin; Kahler, Sven; Khistyaev, Kirill; Kim, Jaehoon; Kis, Gergely; Klunzinger, Phil; Koczor-Benda, Zsuzsanna; Koh, Joong Hoon; Kosenkov, Dimitri; Koulias, Laura; Kowalczyk, Tim; Krauter, Caroline M.; Kue, Karl; Kunitsa, Alexander; Kus, Thomas; Ladjanszki, Istvan; Landau, Arie; Lawler, Keith V.; Lefrancois, Daniel; Lehtola, Susi; Li, Run R.; Li, Yi-Pei; Liang, Jiashu; Liebenthal, Marcus; Lin, Hung-Hsuan; Lin, You-Sheng; Liu, Fenglai; Liu, Kuan-Yu; Loipersberger, Matthias; Luenser, Arne; Manjanath, Aaditya; Manohar, Prashant; Mansoor, Erum; Manzer, Sam F.; Mao, Shan-Ping; Marenich, Aleksandr V.; Markovich, Thomas; Mason, Stephen; Maurer, Simon A.; McLaughlin, Peter F.; Menger, Maximilian F. S. J.; Mewes, Jan-Michael; Mewes, Stefanie A.; Morgante, Pierpaolo; Mullinax, J. Wayne; Oosterbaan, Katherine J.; Paran, Garrette; Paul, Alexander C.; Paul, Suranjan K.; Pavosevic, Fabijan; Pei, Zheng; Prager, Stefan; Proynov, Emil I.; Rak, Adam; Ramos-Cordoba, Eloy; Rana, Bhaskar; Rask, Alan E.; Rettig, Adam; Richard, Ryan M.; Rob, Fazle; Rossomme, Elliot; Scheele, Tarek; Scheurer, Maximilian; Schneider, Matthias; Sergueev, Nickolai; Sharada, Shaama M.; Skomorowski, Wojciech; Small, David W.; Stein, Christopher J.; Su, Yu-Chuan; Sundstrom, Eric J.; Tao, Zhen; Thirman, Jonathan; Tornai, Gabor J.; Tsuchimochi, Takashi; Tubman, Norm M.; Veccham, Srimukh Prasad; Vydrov, Oleg; Wenzel, Jan; Witte, Jon; Yamada, Atsushi; Yao, Kun; Yeganeh, Sina; Yost, Shane R.; Zech, Alexander; Zhang, Igor Ying; Zhang, Xing; Zhang, Yu; Zuev, Dmitry; Aspuru-Guzik, Alan; Bell, Alexis T.; Besley, Nicholas A.; Bravaya, Ksenia B.; Brooks, Bernard R.; Casanova, David; Chai, Jeng-Da; Coriani, Sonia; Cramer, Christopher J.; Cserey, Gyorgy; DePrince, A. Eugene; DiStasio, Robert A.; Dreuw, Andreas; Dunietz, Barry D.; Furlani, Thomas R.; Goddard, William A.; Hammes-Schiffer, Sharon; Head-Gordon, Teresa; Hehre, Warren J.; Hsu, Chao-Ping; Jagau, Thomas-C.; Jung, Yousung; Klamt, Andreas; Kong, Jing; Lambrecht, Daniel S.; Liang, WanZhen; Mayhall, Nicholas J.; McCurdy, C. William; Neaton, Jeffrey B.; Ochsenfeld, Christian; Parkhill, John A.; Peverati, Roberto; Rassolov, Vitaly A.; Shao, Yihan; Slipchenko, Lyudmila V.; Stauch, Tim; Steele, Ryan P.; Subotnik, Joseph E.; Thom, Alex J. W.; Tkatchenko, Alexandre; Truhlar, Donald G.; Van Voorhis, Troy; Wesolowski, Tomasz A.; Whaley, K. Birgitta; Woodcock, H. Lee; Zimmerman, Paul M.; Faraji, Shirin; Gill, Peter M. W.; Head-Gordon, Martin; Herbert, John M.; Krylov, Anna I.Journal of Chemical Physics (2021), 155 (8), 084801CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A review. This article summarizes tech. advances contained in the fifth major release of the Q-Chem quantum chem. program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced d.-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decompn. anal. techniques. High-performance capabilities including multithreaded parallelism and support for calcns. on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design. (c) 2021 American Institute of Physics.
- 47Smith, D. G. A.; Burns, L. A.; Simmonett, A. C.; Parrish, R. M.; Schieber, M. C.; Galvelis, R.; Kraus, P.; Kruse, H.; Di Remigio, R.; Alenaizan, A.; James, A. M. Psi4 1.4: Open-Source Software for High-Throughput Quantum Chemistry. J. Chem. Phys. 2020, 152 (18), 184108, DOI: 10.1063/5.0006002Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXps1Ogsrk%253D&md5=7aaec598ebcd0a728cd43bbba7559602PSI4 1.4: Open-source software for high-throughput quantum chemistrySmith, Daniel G. A.; Burns, Lori A.; Simmonett, Andrew C.; Parrish, Robert M.; Schieber, Matthew C.; Galvelis, Raimondas; Kraus, Peter; Kruse, Holger; Di Remigio, Roberto; Alenaizan, Asem; James, Andrew M.; Lehtola, Susi; Misiewicz, Jonathon P.; Scheurer, Maximilian; Shaw, Robert A.; Schriber, Jeffrey B.; Xie, Yi; Glick, Zachary L.; Sirianni, Dominic A.; O'Brien, Joseph Senan; Waldrop, Jonathan M.; Kumar, Ashutosh; Hohenstein, Edward G.; Pritchard, Benjamin P.; Brooks, Bernard R.; Schaefer, Henry F.; Sokolov, Alexander Yu.; Patkowski, Konrad; DePrince, A. Eugene; Bozkaya, Ugur; King, Rollin A.; Evangelista, Francesco A.; Turney, Justin M.; Crawford, T. Daniel; Sherrill, C. DavidJournal of Chemical Physics (2020), 152 (18), 184108CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)PSI4 is a free and open-source ab initio electronic structure program providing implementations of Hartree-Fock, d. functional theory, many-body perturbation theory, CI, d. cumulant theory, symmetry-adapted perturbation theory, and coupled-cluster theory. Most of the methods are quite efficient, thanks to d. fitting and multi-core parallelism. The program is a hybrid of C + + and Python, and calcns. may be run with very simple text files or using the Python API, facilitating post-processing and complex workflows; method developers also have access to most of PSI4's core functionalities via Python. Job specification may be passed using The Mol. Sciences Software Institute (MolSSI) QCSCHEMA data format, facilitating interoperability. A rewrite of our top-level computation driver, and concomitant adoption of the MolSSI QCARCHIVE INFRASTRUCTURE project, makes the latest version of PSI4 well suited to distributed computation of large nos. of independent tasks. The project has fostered the development of independent software components that may be reused in other quantum chem. programs. (c) 2020 American Institute of Physics.
- 48Helgaker, T.; Klopper, W.; Koch, H.; Noga Basis-set Convergence of Correlated Calculations on Water. J. Chem. Phys. 1997, 106, 9639– 9646, DOI: 10.1063/1.473863Google Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXjvVCgu78%253D&md5=f4689c1b38fe30eb721e9cd7d607bdf7Basis-set convergence of correlated calculations on waterHelgaker, Trygve; Klopper, Wim; Koch, Henrik; Noga, JozefJournal of Chemical Physics (1997), 106 (23), 9639-9646CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The basis-set convergence of the electronic correlation energy in the water mol. is investigated at the second-order Moller-Plesset level and at the coupled-cluster singles-and-doubles level with and without perturbative triples corrections applied. The basis-set limits of the correlation energy are established to within 2mEh by means of (1) extrapolations from sequences of calcns. using correlation-consistent basis sets and (2) from explicitly correlated calcns. employing terms linear in the inter-electronic distances rij. For the extrapolations to the basis-set limit of the correlation energies, fits of the form a + bX-3 (where X is two for double-zeta sets, three for triple-zeta sets, etc.) are found to be useful. CCSD(T) calcns. involving as many as 492 AOs are reported.
- 49Vasilyev, V. Online Complete Basis Set Limit Extrapolation Calculator. Comp. Theor. Chem. 2017, 1115, 1– 3, DOI: 10.1016/j.comptc.2017.06.001Google ScholarThere is no corresponding record for this reference.
- 50Welch, B. K.; Almeida, N. M. S.; Wilson, A. K. Super-ccCA (s-ccCA): An Approach for Accurate Transition Metal Chemistry. Mol. Phys. 2021, 119, e1963001 DOI: 10.1080/00268976.2021.1963001Google ScholarThere is no corresponding record for this reference.
- 51Kreisle, D.; Echt, O.; Knapp, M.; Recknagel, E. Evolution of “Magic Numbers” in Mass Spectra of Clusters After Ionization. Surf. Sci. 1985, 156 (1), 321– 327, DOI: 10.1016/0039-6028(85)90590-4Google ScholarThere is no corresponding record for this reference.
- 52Matro, A.; Freeman, D. L.; Topper, R. Q. Computational Study of the Structures and Thermodynamic Properties of Ammonium Chloride Clusters Using a Parallel Jump-Walking Approach. J. Chem. Phys. 1996, 104, 8690– 8702, DOI: 10.1063/1.471558Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28Xjt1OhsL0%253D&md5=24f03a4187cc6a0370eadd64af66114cComputational study of the structures and thermodynamic properties of ammonium chloride clusters using a parallel jump-walking approachMatro, Alexander; Freeman, David L.; Topper, Robert Q.Journal of Chemical Physics (1996), 104 (21), 8690-8702CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The thermodn. and structural properties of (NH4Cl)n clusters, n = 3-10 are studied. Using the method of simulated annealing, the geometries of several isomers for each cluster size are examd. Jump-walking Monte Carlo simulations are then used to compute the const.-vol. heat capacity for each cluster size over a wide temp. range. To carry out these simulations a new parallel algorithm is developed using the parallel virtual machine (PVM) software package. Features of the cluster potential energy surfaces, such as energy differences among isomers and rotational barriers of the ammonium ions, are found to play important roles in detg. the shape of the heat capacity curves.
- 53Tao, F.-M. Direct Formation of Solid Ammonium Chloride Particles From HCl and NH3 Vapors. J. Chem. Phys. 1999, 110, 11121– 11124, DOI: 10.1063/1.479054Google ScholarThere is no corresponding record for this reference.
- 54Biswakarma, J. J.; Ciocoi, V.; Topper, R. Q. Energetics Thermodynamics, and Hydrogen Bonding Diversity in Ammonium Halide Clusters. J. Phys. Chem. A 2016, 120, 7924– 7934, DOI: 10.1021/acs.jpca.6b06788Google Scholar54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFGrs7rI&md5=b90f5c92202633b8daa65f240c97af81Energetics, Thermodynamics, and Hydrogen Bonding Diversity in Ammonium Halide ClustersBiswakarma, John J.; Ciocoi, Vlad; Topper, Robert Q.Journal of Physical Chemistry A (2016), 120 (40), 7924-7934CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)Contributions from different intermol. and interionic forces, as well as variations in bond energies, produce size-dependent variations in the structures of acid-base mol. clusters. In this work the structures and interaction energetics of cluster particles with the nominal formulas (NH4X)n, X = (F, Cl, Br) are predicted using either "mag-walking" sawtooth simulated annealing Monte Carlo calcns. or model building, followed by M06-2X or RI-MP2 geometry optimization and single-point energy calcns. Whereas the n = 1 clusters all exhibit a single hydrogen bond, small (NH4F)n particles (n = 2-5) exhibit three distinct types of hydrogen bonds as a function of size (traditional, ion-pair and proton-shared). However, (NH4Br)n and (NH4Cl)n particles (n = 2-13) all solely exhibit ion-pair hydrogen bonding, with even values of n exhibiting pronounced relative stability. The computed differential interaction energy of the bromide and chloride systems is generally near the bulk limit of the difference in their accepted lattice energies, despite the fact that their structures do not resemble the bulk crystal structures. Nanoparticle growth reactions are predicted to be thermodynamically spontaneous under std. conditions, with significant size and system dependencies. This work is designed to further our understanding of the nature of hydrogen bonding and other intermol. forces, particularly within ionic nanocrystallites, as well as the thermodn. of cluster formation.
- 55Hendricks, S. B.; Posnjak, E.; Kracek, F. C. Molecular Rotation in the Solid State. The Variation of the Crystal Structure of Ammonium Nitrate with Temperature. J. Am. Chem. Soc. 1932, 54 (7), 2766– 2786, DOI: 10.1021/ja01346a020Google ScholarThere is no corresponding record for this reference.
- 56Rapoport, E.; Pistorius, C. W. F. T. Polymorphism and Melting of Ammonium, Thallous, and Silver Nitrates to 45 kbar. J. Chem. Phys. 1966, 44, 1514– 1519, DOI: 10.1063/1.1726887Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF28XlsF2itQ%253D%253D&md5=0e8bf0792a931131d8e7d172a43123daPolymorphism and melting of ammonium, thallous, and silver nitrates to 45 kilobarsRapoport, Eliezer; Pistorius, Carl W. F. T.Journal of Chemical Physics (1966), 44 (4), 1514-19CODEN: JCPSA6; ISSN:0021-9606.The phase diagrams of NH4NO3 and TlNO3 were detd. by means of differential thermal analysis (DTA) to 40 kilobars. The NH4NO3 I/VI, IV/VI, and I/IV transition lines meet at a triple point near 19.5 kilobars and 256°. The TlNO3 I/II transition line can be represented by t (degrees C.) = 144.6 +7.91P- 0.062P2, and the melting curve of TlNO3 I is given by P (kilobars) = 5.00 [(T/479)3.531 -1]. The phase diagram of AgNO3 was detd. by means of DTA and volumetric methods to 45 kilobars. In addn. to the 4 phases previously known, metastable AgNO3 V can be obtained by suitable manipulation above 21 kilobars at <50°. The metastable AgNO3 I/V transition is easily reversible. AgNO3 V reverts to stable AgNO3 II if left under pressure overnight. The melting curve of AgNO3 II is given by P (kilobars) = 0.17[(T/ 483)4.438-1].
- 57Chellappa, R. S.; Dattelbaum, D. M.; Velisavljevic, N.; Sheffield, S. The Phase Diagram of Ammonium Nitrate. J. Chem. Phys. 2012, 137 (2012), 064504, DOI: 10.1063/1.4733330Google ScholarThere is no corresponding record for this reference.
- 58Kaniewski, M.; Huculak-Maczka, M.; Zielinski, J.; Biegun, M.; Hoffmann, K.; Hoffmann, J. Crystalline Phase Transitions and Reactivity of Ammonium Nitrate in Systems Containing Selected Carbonate Salts. Crystals 2021, 11 (10), 1250, DOI: 10.3390/cryst11101250Google ScholarThere is no corresponding record for this reference.
- 59Lomboy, A. J. A Computational Study of Solvation Effects on Ammonium Nitrate Clusters M.Eng. Dissertation; The Cooper Union for the Advancement of Science and Art, New York, NY, 2020.Google ScholarThere is no corresponding record for this reference.
- 60Fárník, M. Bridging Gaps between Clusters in Molecular Beam Experiments and Aerosol Nanoclusters. J. Phys. Chem. Lett. 2023, 14 (1), 287– 294, DOI: 10.1021/acs.jpclett.2c03417Google ScholarThere is no corresponding record for this reference.
- 61Kubečka, J.; Besel, V.; Neefjes, I.; Knattrup, Y.; Kurtén, T.; Vehkamäki, H.; Elm, J. Computational Tools for Handling Molecular Clusters: Configurational Sampling, Storage, Analysis, and Machine Learning. ACS Omega 2023, 8 (47), 45115– 45128, DOI: 10.1021/acsomega.3c07412Google ScholarThere is no corresponding record for this reference.
- 62Hanwell, M. D.; Curtis, D. E.; Lonie, D. C.; Vandermeersch, T.; Zuek, E.; Hutchison, G. R. Avogadro: An Advanced Semantic Chemical Editor, Visualization, and Analysis Platform. J. Cheminf. 2012, 4 (1), 17, DOI: 10.1186/1758-2946-4-17Google Scholar62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVGksLg%253D&md5=f10400f51db314afa780e99403ca748aAvogadro: an advanced semantic chemical editor, visualization, and analysis platformHanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.; Vandermeersch, Tim; Zurek, Eva; Hutchison, Geoffrey R.Journal of Cheminformatics (2012), 4 (), 17CODEN: JCOHB3; ISSN:1758-2946. (Chemistry Central Ltd.)Background: The Avogadro project has developed an advanced mol. editor and visualizer designed for cross-platform use in computational chem., mol. modeling, bioinformatics, materials science, and related areas. It offers flexible, high quality rendering, and a powerful plugin architecture. Typical uses include building mol. structures, formatting input files, and analyzing output of a wide variety of computational chem. packages. By using the CML file format as its native document type, Avogadro seeks to enhance the semantic accessibility of chem. data types. Results: The work presented here details the Avogadro library, which is a framework providing a code library and application programming interface (API) with three-dimensional visualization capabilities; and has direct applications to research and education in the fields of chem., physics, materials science, and biol. The Avogadro application provides a rich graphical interface using dynamically loaded plugins through the library itself. The application and library can each be extended by implementing a plugin module in C++ or Python to explore different visualization techniques, build/manipulate mol. structures, and interact with other programs. We describe some example extensions, one which uses a genetic algorithm to find stable crystal structures, and one which interfaces with the PackMol program to create packed, solvated structures for mol. dynamics simulations. The 1.0 release series of Avogadro is the main focus of the results discussed here. Conclusions: Avogadro offers a semantic chem. builder and platform for visualization and anal. For users, it offers an easy-to-use builder, integrated support for downloading from common databases such as PubChem and the Protein Data Bank, extg. chem. data from a wide variety of formats, including computational chem. output, and native, semantic support for the CML file format. For developers, it can be easily extended via a powerful plugin mechanism to support new features in org. chem., inorg. complexes, drug design, materials, biomols., and simulations.
- 63Spartan 24 version 1.2.0; Wavefunction, Inc.: Irvine, CA, USA, 2024. https://www.wavefun.com/. accessed 2024 July 09.Google ScholarThere is no corresponding record for this reference.
- 64TransRot version 1.6.4; The Cooper Union for the Advancement of Science and Art: New York, NY, USA,2024. https://github.com/steventopper/TransRot. accessed 2024 July 09.Google ScholarThere is no corresponding record for this reference.
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Abstract
Figure 1
Figure 1. (NH3–HNO3)and (NH4HNO3)2 structures at the ωB97X-D3/def2-SVPD level of theory.
Figure 2
Figure 2. [(NH4)2NO3]+ (upper) and (lower) structures optimized at the ωB97X-D3/def2-SVPD level of theory and those reported by Dunlap and Doyle (23) using the BP functional (right). Adapted from 23. Copyright 1996 American Chemical Society.
Figure 3
Figure 3. Positive-ion sputtered mass spectrum of ammonium nitrate clusters. (23) Predicted ωB97X-D3 structures of parent and daughter ions corresponding to the numbered peaks have been added to the original spectrum. Adapted from 23. Copyright 1996 American Chemical Society.
Figure 4
Figure 4. ωB97X-D3 electronic binding energies for different fragmentation channels of .
Figure 5
Figure 5. ωB97X-D3 and OPLS/TR differential interaction energies for the parents.
Figure 6
Figure 6. Negative-ion sputtered mass spectrum of ammonium nitrate clusters. (23) Predicted structures of parent ions corresponding to the numbered peaks have been added to the original spectrum. Adapted from 23. Copyright 1996 American Chemical Society.
Figure 7
Figure 7. ωB97X-D3 electronic binding energies for different fragmentation channels of cations.
Figure 8
Figure 9
Figure 9. ωB97X-D3 (DFT) and OPLS/TR differential interaction energies for the parents.
Figure 10
Figure 10. Predicted structures of selected (NH4NO3)n nanoparticles from OPLS/TR calculations followed by ωB97X-D3/def2-SVPD geometry optimization.
Figure 11
Figure 11. ωB97X-D3 differential interaction energies for (NH4NO3)n from OPLS-AA (black) and ωB97X-D3/def2-TZPD calculations (blue). Also shown: ωB97X-D3 calculations using a 6-311+G(2df,2p)[6-311G(d)] “Pople” basis; see text (orange). The optimized n = 4, 6, 9, 16, 21, 27, and 37 structures are shown.
References
This article references 64 other publications.
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- 3Haywood, J.; Boucher, O. Estimates of the Direct and Indirect Radiative Forcing Due To Tropospheric Aerosols: A Review. Rev. Geophys. 2000, 38, 513– 543, DOI: 10.1029/1999RG0000783https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXosFSlsr8%253D&md5=f56ce1f9e5cfef3da50afdf5991c443dEstimates of the direct and indirect radiative forcing due to tropospheric aerosols: a reviewHaywood, James; Boucher, OlivierReviews of Geophysics (2000), 38 (4), 513-543CODEN: REGEEP; ISSN:8755-1209. (American Geophysical Union)A review with 209 refs. concerning developments in estg. direct and indirect global annual mean radiative forcing due to present-day anthropogenic tropospheric aerosol concns. since the Inter-governmental Panel on Climate Change (1996) is given. Topics discussed include: direct radiative forcing (detg. direct radiative forcing, SO42- aerosols, carbon black and org. C [fossil fuel, biomass burning, other studies], mineral dust aerosol, NO3- aerosol, mixed aerosols, field campaigns, satellite measurements, discussion of uncertainties of direct effect); indirect radiative forcing (SO42- aerosols [estg. cloud albedo effect, estg. cloud lifetime effect and combined effects, model evaluation, further discussion of uncertainties], other aerosol species [carbonaceous, combined SO42- and carbonaceous, mineral dust, gas phase HNO3 effect], other methods to est. indirect aerosol effect [missing climate forcing, remote sensing of indirect effects of aerosols], aerosol indirect effect on ice clouds [contrails and contrail-induced cloudiness, impact of aircraft exhaust on cirrus cloud micro-phys., effect of anthropogenic aerosols emitted at the surface of ice clouds]); and conclusions.
- 4Liu, L.; Li, H.; Zhang, H.; Zhong, J.; Bai, Y.; Ge, M.; Li, Z.; Chen, Y.; Zhang, X. The Role of Nitric Acid in Atmospheric New Particle Formation. Phys. Chem. Chem. Phys. 2018, 20, 17406– 17414, DOI: 10.1039/C8CP02719F4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVGgurvM&md5=1e5d140bb3506da3f3d8591c962e478bThe role of nitric acid in atmospheric new particle formationLiu, Ling; Li, Hao; Zhang, Haijie; Zhong, Jie; Bai, Yang; Ge, Maofa; Li, Zesheng; Chen, Yu; Zhang, XiuhuiPhysical Chemistry Chemical Physics (2018), 20 (25), 17406-17414CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Nitric acid, an air pollutant with strong acidity and oxidizability, can be found in considerable quantities in the gas and aerosol phase. Understanding the role of nitric acid in atm. new particle formation is essential to study the complicated nucleation mechanism. Using d. functional theory combined with the Atm. Clusters Dynamic Code (ACDC), the role of nitric acid in the formation of new particles has been investigated under different atm. conditions (different precursor concns. and temps.). The results show that nitric acid can form clusters with sulfuric acid and ammonia by hydrogen bond or even proton-transfer interactions. The concns. of clusters involving nitric acid can be comparable with those of sulfuric acid-ammonia-based clusters, considering the thermodn. stability combined with the realistic atm. concns. of precursors. Within the atm. concn. range, nitric acid can enhance the formation rates of sulfuric acid-ammonia clusters, esp. at low temp., low sulfuric acid concn. and high ammonia concn. In addn., the new particle formation mechanism indicates that nitric acid can contribute to the cluster formation and the role of nitric acid in the cluster formation pathway is as a "bridge" connecting the smaller and larger clusters.
- 5Chee, S.; Barsanti, K.; Smith, J. N.; Myllys, N. A Predictive Model for Salt Nanoparticle Formation Using Heterodimer Stability Calculations. Atmos. Chem. Phys. 2021, 21, 11637– 11654, DOI: 10.5194/acp-21-11637-20215https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvFWhtbzE&md5=79bc95e833ac430a15012709829250faA predictive model for salt nanoparticle formation using heterodimer stability calculationsChee, Sabrina; Barsanti, Kelley; Smith, James N.; Myllys, NannaAtmospheric Chemistry and Physics (2021), 21 (15), 11637-11654CODEN: ACPTCE; ISSN:1680-7324. (Copernicus Publications)The best predictor of heterodimer stability was found to be gas-phase acidity. We then analyzed the relationship between heterodimer stability and J4 x 4, the theor. predicted formation rate of a four-acid, four-base cluster, for sulfuric acid salts over a range of monomer concns. from 105 to 109 molec cm-3 and temps. from 248 to 348 K and found that heterodimer stability forms a lognormal relationship with J4 x 4. However, temp. and concn. effects made it difficult to form a predictive expression of J4 x 4. In order to reduce those effects, heterodimer concn. was calcd. from heterodimer stability and yielded an expression for predicting J4 x 4 for any salt, given approx. equal acid and base monomer concns. and knowledge of monomer concn. and temp. This parameterization was tested for the sulfuric acid-ammonia system by comparing the predicted values to exptl. data and was found to be accurate within 2 orders of magnitude. We show that one can create a simple parameterization that incorporates the dependence on temp. and monomer concn. on J4 x 4 by defining a new term that we call the normalized heterodimer concn., Φ. A plot of J4 x 4 vs. Φ collapses to a single monotonic curve for weak sulfate salts (difference in gas-phase acidity >95 kcal mol-1) and can be used to accurately est. J4 x 4 within 2 orders of magnitude in atm. models.
- 6Du, W.; Cai, J.; Zheng, F.; Yan, C.; Zhou, Y.; Guo, Y.; Chu, B.; Yao, L.; Heikkinen, L. M.; Fan, X. Influence of Aerosol Chemical Composition on Condensation Sink Efficiency and New Particle Formation in Beijing. Environ. Sci. Technol. Lett. 2022, 9, 375– 382, DOI: 10.1021/acs.estlett.2c001596https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XptlGltb8%253D&md5=f2588c433689d14a004c5f899516774cInfluence of Aerosol Chemical Composition on Condensation Sink Efficiency and New Particle Formation in BeijingDu, Wei; Cai, Jing; Zheng, Feixue; Yan, Chao; Zhou, Ying; Guo, Yishuo; Chu, Biwu; Yao, Lei; Heikkinen, Liine M.; Fan, Xiaolong; Wang, Yonghong; Cai, Runlong; Hakala, Simo; Chan, Tommy; Kontkanen, Jenni; Tuovinen, Santeri; Petaja, Tuukka; Kangasluoma, Juha; Bianchi, Federico; Paasonen, Pauli; Sun, Yele; Kerminen, Veli-Matti; Liu, Yongchun; Daellenbach, Kaspar R.; Dada, Lubna; Kulmala, MarkkuEnvironmental Science & Technology Letters (2022), 9 (5), 375-382CODEN: ESTLCU; ISSN:2328-8930. (American Chemical Society)Relatively high concns. of preexisting particles, acting as a condensation sink (CS) of gaseous precursors, have been thought to suppress the occurrence of new particle formation (NPF) in urban environments, yet NPF still occurs frequently. Here, we aim to understand the factors promoting and inhibiting NPF events in urban Beijing by combining one-year-long measurements of particle no. size distributions and PM2.5 chem. compn. Our results show that indeed the CS is an important factor controlling the occurrence of NPF events, with its chem. compn. affecting the efficiency of the background particles in removing gaseous H2SO4 (effectiveness of the CS) driving NPF. During our observation period, the CS was found to be more effective for ammonium nitrate-rich (NH4NO3-rich) fine particles. On non-NPF event days, particles acting as CS contained a larger fraction of NH4NO3 compared to NPF event days under comparable CS levels. In particular, in the CS range from 0.02 to 0.03 s-1, the nitrate fraction was 17% on NPF event days and 26% on non-NPF event days. Overall, our results highlight the importance of considering the chem. compn. of preexisting particles when estg. the CS and their role in inhibiting NPF events, esp. in urban environments.
- 7Brown, S. S.; Baasandorj, M. Utah Winter Fine Particulate Study (UWFPS White Paper), NOAA, 2017, https://csl.noaa.gov/groups/csl7/measurements/2017uwfps/.There is no corresponding record for this reference.
- 8Lammel, G.; Pohlmann, G. Phase Behaviour of Ammonia, Nitric Acid and Particulate Ammonium Nitrate: The Influence of the Aerosol Characteristics. J. Aerosol Sci. 1992, 23, 941– 944, DOI: 10.1016/0021-8502(92)90567-F8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXktFCgu7w%253D&md5=bdc20497c8de5d65144f6c0d4abbdf67Phase behavior of ammonia, nitric acid and particulate ammonium nitrate: the influence of the aerosol characteristicsLammel, G.; Pohlmann, G.Journal of Aerosol Science (1992), 23 (Suppl. 1), S941-S944CODEN: JALSB7; ISSN:0021-8502.In a field study of NH3 and HNO3 phase partitioning, aerosol characteristics, i.e., size distributions, were considered in addn. to concns. of chem. species involved for the first time. Deviations from equil. are discussed in the context of degree of mixing. From estns. of particulate NH4NO3 surface to vol. ratio, an interdependence of the attainment of the interphase equil. and the interfacial area is indicated.
- 9Behera, S. N.; Sharma, M.; Aneja, V. P.; Balasubramanian, R. Ammonia in the Atmosphere: A Review on Emission Sources, Atmospheric Chemistry and Deposition on Terrestrial Bodies. Environ. Sci. Pollut. Res. 2013, 20, 8092– 8131, DOI: 10.1007/s11356-013-2051-99https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhs1eltbzO&md5=0ace894359c42eb6578483750a29b76bAmmonia in the atmosphere: a review on emission sources, atmospheric chemistry and deposition on terrestrial bodiesBehera, Sailesh N.; Sharma, Mukesh; Aneja, Viney P.; Balasubramanian, RajasekharEnvironmental Science and Pollution Research (2013), 20 (11), 8092-8131CODEN: ESPLEC; ISSN:0944-1344. (Springer)A review. Gaseous ammonia (NH3) is the most abundant alk. gas in the atm. In addn., it is a major component of total reactive nitrogen. The largest source of NH3 emissions is agriculture, including animal husbandry and NH3-based fertilizer applications. Other sources of NH3 include industrial processes, vehicular emissions and volatilization from soils and oceans. Recent studies have indicated that NH3 emissions have been increasing over the last few decades on a global scale. This is a concern because NH3 plays a significant role in the formation of atm. particulate matter, visibility degrdn. and atm. deposition of nitrogen to sensitive ecosystems. Thus, the increase in NH3 emissions neg. influences environmental and public health as well as climate change. For these reasons, it is important to have a clear understanding of the sources, deposition and atm. behavior of NH3. Over the last two decades, a no. of research papers have addressed pertinent issues related to NH3 emissions into the atm. at global, regional and local scales. This review article integrates the knowledge available on atm. NH3 from the literature in a systematic manner, describes the environmental implications of unabated NH3 emissions and provides a scientific basis for developing effective control strategies for NH3.
- 10El Sayed, M. J. Beirut Ammonium Nitrate Explosion: A Man-made Disaster in Times of the COVID-19 Pandemic. Disaster Med. Public Health Prep. 2022, 16 (3), 1203– 1207, DOI: 10.1017/dmp.2020.451There is no corresponding record for this reference.
- 11Feick, G.; Hainer, R. M. On the Thermal Decomposition of Ammonium Nitrate. Steady-state Reaction Temperatures and Reaction Rate. J. Am. Chem. Soc. 1954, 76 (22), 5860– 5863, DOI: 10.1021/ja01651a09611https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG2MXhsVKgsg%253D%253D&md5=d14013d851deb91615c10071e26c493fThermal decomposition of ammonium nitrate. Steady-state reaction temperatures and reaction rateFeick, George; Hainer, R. M.Journal of the American Chemical Society (1954), 76 (), 5860-3CODEN: JACSAT; ISSN:0002-7863.Molten NH4NO3 reaches a steady-state temp. as a result of the irreversible exothermic decompn. (I) to N2O(g) and 2H2O(g), and the reversible endothermic dissocn. (II) to NH3(g) and HNO3(g). The relation P = {1 + [(3/2)ΔHv/(Q - ΔHr)] }p is derived, where P is the ambient pressure, p is the dissocn. pressure, ΔHr and ΔHv are the heats of I and II, resp., and Q is the heat added to the system per mole NH4NO3 decompd. ΔHr is calcd. from published data to be -13.21 and -14.58 kcal./mole at 169.6 and 300°, resp. Values of p and ΔHv up to about 250° were given by F. (preceding abstr.). From 250 to 350° the equation log p (cm.) = - (4109/T) + 8.502 is used to obtain p. Measurement of P and Q suffice to det. p, and thus to define the temp. of the melt. Exptl. detn. of the steady-state temp. for the adiabatic case (Q = 0) agrees with predicted values; this temp. is 271° at 38 cm., and 315° at 152 cm. total pressure. The over-all rate const. for I and II at 290° and 1 atm. is 2.3 × 10-3/sec., and for I alone the rate const. is 1.64 × 10-3/sec. The latter value is compared with 12.6 × 10-3/sec. obtained by Robertson (C.A. 43, 405c).
- 12Brandner, J. D.; Junk, N. M.; Lawrence, J. W.; Robins, J. Vapor Pressure of Ammonium Nitrate. J. Chem. Eng. Data 1962, 7 (2), 227– 228, DOI: 10.1021/je60013a020There is no corresponding record for this reference.
- 13Nguyen, M.-T.; Jamka, A. J.; Cazar, R. A.; Tao, F.-M. Structure and Stability of the Nitric Acid–Ammonia Complex in the Gas Phase and in Water. J. Chem. Phys. 1997, 106, 8710– 8717, DOI: 10.1063/1.47392513https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXjsV2rsb0%253D&md5=aad8357ebd1dafbe5271f6b2c08b4648Structure and stability of the nitric acid-ammonia complex in the gas phase and in waterNguyen, Minh-Tuan; Jamka, Alan J.; Cazar, Robert A.; Tao, Fu-MingJournal of Chemical Physics (1997), 106 (21), 8710-8717CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The nitric acid-ammonia system is studied by high level ab initio calcns. The equil. structure, vibrational frequencies, and binding energy of the system in the gas phase are calcd. at the second-order Moller-Plesset perturbation level with the extended basis set 6-311 + +G(d,p). The potential energy surface along the proton transfer pathway is investigated by calcns. at the same level of theory, and the effect of water as a solvent on the structure and stability of the system is investigated using self-consistent reaction field theory. It is found that the equil. structure contains a strong hydrogen bond with nitric acid acting as the hydrogen bond donor and ammonia as the acceptor. The binding energy is calcd. to be D0=12.25 kcal/mol (De=14.26 kcal/mol), which is about three times greater than the binding energy for the water dimer. The OH stretching frequency of nitric acid in the hydrogen-bonded complex is found to be red shifted by over 800 cm-1, with an enhancement of over an order of magnitude in the IR intensity from the isolated nitric acid mol. The structure of ammonium nitrate corresponding to the product of a proton transfer reaction is found to be highly unstable on the potential energy surface. The most energetically favorable gas phase reaction of nitric acid and ammonia in the absence of a solvent results in proton exchange, not proton transfer from acid to base. The structure and stability of the system change drastically in the water solvent medium. In the water solvent, the hydrogen-bonded structure is no longer stable and the system exists as an ammonium nitrate ion pair resulting from the completed transfer of a proton from nitric acid to ammonia. On the basis of these results, we conclude that it is unlikely to form gaseous ammonium nitrate from nitric acid and ammonia, and that the formation of particulate ammonium nitrate most likely involves a heterogeneous mechanism.
- 14Dimitrova, Y.; Peyerimhoff, S. D. Ab Initio Study of Structures of Hydrogen-bonded Nitric Acid Complexes. Chem. Phys. 2000, 254, 125– 134, DOI: 10.1016/S0301-0104(00)00024-0There is no corresponding record for this reference.
- 15Alavi, S.; Thompson, D. L. Theoretical Study of Proton Transfer in Ammonium Nitrate Clusters. J. Chem. Phys. 2002, 117 (6), 2599– 2608, DOI: 10.1063/1.1489995There is no corresponding record for this reference.
- 16Chien, W.-M.; Chandra, D.; Lau, K. H.; Hildenbrand, D. L.; Helmy, A. M. The Vaporization of NH4NO3. J. Chem. Thermodyn. 2010, 42, 846– 651, DOI: 10.1016/j.jct.2010.01.01216https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXlsVGjtL4%253D&md5=d77abcc966f9e3163d0e00e8f534b1c7The vaporization of NH4NO3Chien, Wen-Ming; Chandra, Dhanesh; Lau, K.-H.; Hildenbrand, D. L.; Helmy, A. M.Journal of Chemical Thermodynamics (2010), 42 (7), 846-851CODEN: JCTDAF; ISSN:0021-9614. (Elsevier Ltd.)The total vapor pressure and vapor mol. wt. of ammonium nitrate (NH4NO3) were detd. The vapor pressure was detd. by the torsion + effusion method, and vapor compn. was detd. by effusion-beam mass spectrometry. Total vapor pressures of NH4NO3 were measured by using two effusion cells with different orifice diams. over the pressure range of 10-6 to 10-3 kPa between 313 and 360 K. The equil. vapor pressure equation was zero-extrapolated from measurements with different orifice Knudsen cells, P1 and P2 cells, and is given as: log PT (kPa) = (10.400 ± 0.0002) - (4783.16 ± 0.07)/T. The measured mol. wt. of NH4NO3 is 48.7 g/mol for P1 cell and 50.7 g/mol for P2 cell, both of which are much less than the theor. mol. wt. of NH4NO3 (approx. 80.04 g/mol). This significant difference in mol. wt. suggests that there is disproportionation of NH4NO3 samples. The mass spectroscopic results revealed that NH4NO3 decomps. to NH3 and HNO3; it was interesting to note that the expected N2, O2, and H2O gases were not evolved during vaporization. The partial pressures of the three gas phase species (NH4NO3, NH3, and HNO3) that were evolved during vaporization of NH4NO3 sample were detd. as: P1 cell: PNH4NO3/PT = 0.1490, PNH3/PT = 0.2911, and PHNO3/PT = 0.5599, and P2 cell: PNH4NO3/PT = 0.2101, PNH3/PT = 0.2702, and PHNO3/PT = 0.5197. The std. Gibbs energy change (ΔG°) for NH4NO3 decompn. and sublimation reactions are obtained from the partial pressure results. Details of total and partial pressures of vaporization of NH4NO3 and disproportionation aspects of the evolved gases are presented.
- 17Hildenbrand, D. L.; Lau, K. H.; Chandra, D. Thermochemistry of Gaseous Ammonium Nitrate, NH4NO3 (g). J. Chem. Phys. A 2010, 114, 111654– 111655, DOI: 10.1021/jp105773qThere is no corresponding record for this reference.
- 18Irikura, K. K. Thermochemistry of Ammonium Nitrate, NH4NO3, in the Gas Phase. J. Phys. Chem. A 2010, 114, 11651– 11653, DOI: 10.1021/jp105770d18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXht1KhsLbL&md5=78893cfed35759afefd7a7b3a160b1b5Thermochemistry of Ammonium Nitrate, NH4NO3, in the Gas PhaseIrikura, Karl K.Journal of Physical Chemistry A (2010), 114 (43), 11651-11653CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)Hildenbrand and co-workers have shown recently that the vapor above solid ammonium nitrate includes mols. of NH4NO3, not only NH3 and HNO3 as previously believed. Their measurements led to thermochem. values that imply an enthalpy change of D298 = 98 ± 9 kJ mol-1 for the gas-phase dissocn. of ammonium nitrate into NH3 and HNO3. Using updated spectroscopic information for the partition function leads to the revised value of D298 = 78 ± 21 kJ mol-1 (accompanying paper in this journal, Hildenbrand, D. L.; Lau, K. H.; Chandra, D. J. Phys. Chem. B2010, DOI: 10.1021/jp105773q00080533A). In contrast, high-level ab initio calcns., detailed in the present report, predict a dissocn. enthalpy half as large as the original result, 50 ± 3 kJ mol-1. These are frozen-core CCSD(T) calcns. extrapolated to the limiting basis set aug-cc-pV∞Z using an anharmonic vibrational partition function and a variational treatment of the NH3 rotor. The corresponding enthalpy of formation is ΔfH298°(NH4NO3,g) = -230.6 ± 3 kJ mol-1. The origin of the disagreement with expt. remains unexplained.
- 19Marechal, Y. The Hydrogen Bond and the Water Molecule; Elsevier: Amsterdam, 2007.There is no corresponding record for this reference.
- 20Takeuchi, J.; Masuda, Y.; Clark, R.; Takeda, K. Theoretical Studies on Proton Transfer in Ammonium Nitrate Monomer and Dimer. Japanese J. Appl. Phys. 2013, 52 (7R), 076302, DOI: 10.7567/JJAP.52.076302There is no corresponding record for this reference.
- 21Cagnina, S.; Rotureau, P.; Fayet, G.; Adamo, C. The Ammonium Nitrate and Its Mechanism of Decomposition in the Gas Phase: A Theoretical Study and a DFT Benchmark. Phys. Chem. Chem. Phys. 2013, 15, 10849– 10858, DOI: 10.1039/c3cp50368b21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXptFCntLw%253D&md5=f349b1d73474bc6601969020e71a9cf7The ammonium nitrate and its mechanism of decomposition in the gas phase: a theoretical study and a DFT benchmarkCagnina, Stefania; Rotureau, Patricia; Fayet, Guillaume; Adamo, CarloPhysical Chemistry Chemical Physics (2013), 15 (26), 10849-10858CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)The decompn. mechanism of ammonium nitrate in the gas phase was investigated and fully characterized by means of CBS-QB3 calcns. Five reaction channels were identified, leading to the formation of products (N2, H2O, O2, OH, HNO, NO3) found in the exptl. works. The identified mechanism well underlines the origin of the chem. hazard of ammonium nitrate which is related to the exothermicity of the lowest decompn. channels. Furthermore, the high barrier to overcome in the rate detg. step well explained the fact that the reaction is not usually spontaneous and requires a significant external stimulus for its onset. An accurate DFT benchmark study was then conducted to det. the most suitable exchange-correlation functional to accurately describe the reaction profile both in terms of structures and thermochem. This evaluation supports the use of the M06-2X functional as the best option for the study of ammonium nitrate decompn. and related reactions. Indeed, this level of theory provided the lowest deviations with respect to CBS-QB3 ref. values, outperforming functionals esp. developed for reaction kinetics.
- 22Ling, J.; Ding, X.; Li, Z.; Yang, J. First-Principles Study of Molecular Clusters Formed by Nitric Acid and Ammonia. J. Phys. Chem. A 2019, 121, 661– 668, DOI: 10.1021/acs.jpca.6b09185There is no corresponding record for this reference.
- 23Dunlap, B. I.; Doyle, R. J. J. Ammonium Nitrate Cluster Ions. J. Phys. Chem. 1996, 100, 5281– 5285, DOI: 10.1021/jp951675523https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XhsVGgtLc%253D&md5=4b85e764db960a5356167638022e716cAmmonium Nitrate Cluster IonsDunlap, Brett I.; Doyle, Robert J., Jr.Journal of Physical Chemistry (1996), 100 (13), 5281-5CODEN: JPCHAX; ISSN:0022-3654. (American Chemical Society)Sputtering of condensed-phase ammonium nitrate yields many pos. and neg. cluster ion series derived from different ionic cores. The cluster cores are surrounded by varying nos. of ammonium nitrate monomer units. Most interesting is the extensive series of neg. cluster ions of the form [(NH4NO3)nNO3]-, n ≥ 3. The corresponding pos. clusters, [(NH4NO3)nNH4]+, are also very extensive but also include the smallest ions, n = 1 and 2. Collision-induced dissocn. of mass-selected cluster ions suggests that the first two members of the neg. series, n = 1 and n = 2, are not detected because they rearrange and lose one or more ammonia mols. Gradient-d.-functional calcns. using two different functionals predict that NH4NO3 is strongly hydrogen bonded and that [(NH4NO3)NO3]- has no hydrogen bonds. This is consistent with this ion rearranging by loss of NH3 to form the strongly hydrogen-bonded ion [H(NO3)2]-. Rearrangements involving loss of ammonia mols. in the neg.-ion spectrum and nitric acid mols. in the pos.-ion spectrum lead to a rich variety of other, less extensive, series of sputtered ions from this complex solid. Both relative gradient-d.-functional energies correlate well with whether or not various ions are observable exptl.
- 24Lin, Y.; Li, G.; Mao, S.; Chai, J. Long-range Corrected Hybrid Density Functionals With Improved Dispersion Corrections. J. Chem. Theory Comput. 2013, 9, 263– 272, DOI: 10.1021/ct300715s24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xhs1WltLrP&md5=8b6cf43f9d58e66754405fb28fd70438Long-Range Corrected Hybrid Density Functionals with Improved Dispersion CorrectionsLin, You-Sheng; Li, Guan-De; Mao, Shan-Ping; Chai, Jeng-DaJournal of Chemical Theory and Computation (2013), 9 (1), 263-272CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)By incorporating the improved empirical atom-atom dispersion corrections from DFT-D3 [Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys.2010, 132, 154104], two long-range cor. (LC) hybrid d. functionals are proposed. Our resulting LC hybrid functionals, ωM06-D3 and ωB97X-D3, are shown to be accurate for a very wide range of applications, such as thermochem., kinetics, noncovalent interactions, frontier orbital energies, fundamental gaps, and long-range charge-transfer excitations, when compared with common global and LC hybrid functionals. Relative to ωB97X-D [Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys.2008, 10, 6615], ωB97X-D3 (reoptimization of ωB97X-D with improved dispersion corrections) is shown to be superior for nonbonded interactions, and similar in performance for bonded interactions, while ωM06-D3 is shown to be superior for general applications.
- 25Topper, R. Q.; Topper, S. L.; Lee, S. TransRot: A Portable Software Package for Simulated Annealing Monte Carlo Geometry Optimization of Atomic and Molecular Clusters. In ACS Symposium Series, Parish, C.A.; Hopkins, T.A., Eds.; ACS Publications: Washington DC, 2022; Vol. 1428; pp. 19 38. DOI: 10.1021/bk-2022-1428.ch002 .There is no corresponding record for this reference.
- 26Jorgensen, W. L.; Maxwell, D. S.; Tirado-Rives, J. Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids. J. Am. Chem. Soc. 1996, 118, 11225– 11236, DOI: 10.1021/ja962176026https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XmtlOitrs%253D&md5=fef2924a69421881390282aa309ae91bDevelopment and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic LiquidsJorgensen, William L.; Maxwell, David S.; Tirado-Rives, JulianJournal of the American Chemical Society (1996), 118 (45), 11225-11236CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The parametrization and testing of the OPLS all-atom force field for org. mols. and peptides are described. Parameters for both torsional and nonbonded energetics have been derived, while the bond stretching and angle bending parameters have been adopted mostly from the AMBER all-atom force field. The torsional parameters were detd. by fitting to rotational energy profiles obtained from ab initio MO calcns. at the RHF/6-31G*//RHF/6-31G* level for more than 50 org. mols. and ions. The quality of the fits was high with av. errors for conformational energies of less than 0.2 kcal/mol. The force-field results for mol. structures are also demonstrated to closely match the ab initio predictions. The nonbonded parameters were developed in conjunction with Monte Carlo statistical mechanics simulations by computing thermodn. and structural properties for 34 pure org. liqs. including alkanes, alkenes, alcs., ethers, acetals, thiols, sulfides, disulfides, aldehydes, ketones, and amides. Av. errors in comparison with exptl. data are 2% for heats of vaporization and densities. The Monte Carlo simulations included sampling all internal and intermol. degrees of freedom. It is found that such non-polar and monofunctional systems do not show significant condensed-phase effects on internal energies in going from the gas phase to the pure liqs.
- 27Jorgensen, W. L.; Tirado-Rives, J. Molecular Modeling of Organic and Biomolecular Systems Using BOSS and MCPRO. J. Comput. Chem. 2005, 26, 1689– 1700, DOI: 10.1002/jcc.2029727https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXht1SlsbbN&md5=e487e9838d39e4b39a5d06a240bfc1e0Molecular modeling of organic and biomolecular systems using BOSS and MCPROJorgensen, William L.; Tirado-Rives, JulianJournal of Computational Chemistry (2005), 26 (16), 1689-1700CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)An overview is provided of the capabilities for the current versions of the BOSS and MCPRO programs for mol. modeling of org. and biomol. systems. Recent applications are noted, particularly for QM/MM studies of org. and enzymic reactions and for protein-ligand binding.
- 28Tinker version 8.11; Washington University in St. Louis: St: Louis, MO, USA, 2024. https://dasher.wustl.edu/tinker/. accessed August 28, 2024.There is no corresponding record for this reference.
- 29Topper, R. Q.; Freeman, D. L.; Bergin, D.; LaMarche, K. Computational Techniques and Strategies for Monte Carlo Thermodynamic Calculations With Applications to Nanoclusters. In Reviews in Computational Chemistry ISBN 0–471–23585–7, Lipkowitz, K. B.; Larter, R.; Cundari, T.R., Eds.; Wiley-VCH/John Wiley and Sons: New York, 2003; Vol. 19, pp. 1 41.There is no corresponding record for this reference.
- 30Torres, F. M.; Agichtein, E.; Grinberg, L.; Yu, G.; Topper, R. Q. A Note on the Application of the “Boltzmann Simplex”-Simulated Annealing Algorithm to Global Optimizations of Argon and Water Clusters. J. Mol. Struct. (THEOCHEM) 1997, 419, 85– 95, DOI: 10.1016/S0166-1280(97)00195-430https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXmvFCkug%253D%253D&md5=d31fd6733a352aa82b87bdc30a9c2faaA note on the application of the "Boltzmann simplex"-simulated annealing algorithm to global optimizations of argon and water clustersTorres, Francis M.; Agichtein, Eugene; Grinberg, Leonid; Yu, Guowei; Topper, Robert Q.Journal of Molecular Structure: THEOCHEM (1997), 419 (), 85-95CODEN: THEODJ; ISSN:0166-1280. (Elsevier Science B.V.)We report our application of a recently published simulated annealing algorithm which we call "Boltzmann simplex"-simulated annealing (BSSA) to global optimizations of argon and water clusters. The Lennard-Jones model of argon clusters serves as a challenging benchmark for global optimization methods, and we use it as a test case. The BSSA method is most useful when followed by a local optimization via the Powell method. This is because the Powell method quenches to the equil. geometry more effectively than a downhill simplex, which is the zero-temp. limit of the BSSA algorithm. We also find that very slow annealing rates are required to achieve acceptable results. A study of small water clusters [(H2O)m, m = 2-6] using a recently published flexible-monomer interaction potential yields ring-like structures which are in good agreement with other theor. and exptl. studies for m = 3-5. A highly puckered ring structure is obtained for m = 6.
- 31Digges, T. G.; Rosenberg, S. J.; Geil, G. W. Heat Treatment And Properties Of Iron And Steel, National Bureau of Standards Monograph 88, 1966, https://nvlpubs.nist.gov/nistpubs/legacy/mono/nbsmonograph88.pdf.There is no corresponding record for this reference.
- 32Leary, R. H. Global Optimization on Funneling Landscapes. J. Global Optim. 2000, 18, 367– 383, DOI: 10.1023/A:1026500301312There is no corresponding record for this reference.
- 33Locatelli, M.; Schoen, F. Efficient Algorithms for Large Scale Global Optimization: Lennard-Jones Clusters. Comput. Optim. Appl. 2003, 26, 173– 190, DOI: 10.1023/A:1025798414605There is no corresponding record for this reference.
- 34Wales, D. J.; Doye, J. P. K. Global Optimization by Basin-Hopping and the Lowest Energy Structures of Lennard-Jones Clusters Containing Up to 110 Atoms. J. Phys. Chem. A 1997, 101, 5111– 5116, DOI: 10.1021/jp970984n34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXktVGrurY%253D&md5=f40693ff24b5c84a8c482fa18ec1eb47Global Optimization by Basin-Hopping and the Lowest Energy Structures of Lennard-Jones Clusters Containing up to 110 AtomsWales, David J.; Doye, Jonathan P. K.Journal of Physical Chemistry A (1997), 101 (28), 5111-5116CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)We describe a global optimization technique using "basin-hopping" in which the potential energy surface is transformed into a collection of interpenetrating staircases. This method has been designed to exploit the features that recent work suggests must be present in an energy landscape for efficient relaxation to the global min. The transformation assocs. any point in configuration space with the local min. obtained by a geometry optimization started from that point, effectively removing transition state regions from the problem. However, unlike other methods based upon hypersurface deformation, this transformation does not change the global min. The lowest known structures are located for all Lennard-Jones clusters up to 110 atoms, including a no. that have never been found before in unbiased searches.
- 35González, B. S.; Noya, E. G.; Vega, C.; Sesé, L. M. Nuclear Quantum Effects in Water Clusters: The Role of the Molecular Flexibility. J. Phys. Chem. B 2010, 114, 2484– 2492, DOI: 10.1021/jp910770y35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtlCgt7w%253D&md5=acd19d381a4c4e6d367bea544e43ee97Nuclear Quantum Effects in Water Clusters: The Role of the Molecular FlexibilityGonzalez, Briesta S.; Noya, Eva G.; Vega, Carlos; Sese, Luis M.Journal of Physical Chemistry B (2010), 114 (7), 2484-2492CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)With the objective of establishing the importance of water flexibility in empirical models which explicitly include nuclear quantum effects, we have carried out path integral Monte Carlo simulations in water clusters with up to seven mols. Two recently developed models have been used for comparison: the rigid TIP4PQ/2005 and the flexible q-TIP4P/F models, both inspired by the rigid TIP4P/2005 model. To obtain a starting configuration for our simulations, we have located the global min. for the rigid TIP4P/2005 and TIP4PQ/2005 models and for the flexible q-TIP4P/F model. All the structures are similar to those predicted by the rigid TIP4P potential showing that the charge distribution mainly dets. the global min. structure. For the flexible q-TIP4P/F model, we have studied the geometrical distortion upon isotopic substitution by studying tritiated water clusters. Our results show that tritiated water clusters exhibit an rOT distance shorter than the rOH distance in water clusters, not significant changes in the ΦHOH angle, and a lower av. dipole moment than water clusters. We have also carried out classical simulations with the rigid TIP4PQ/2005 model showing that the rotational kinetic energy is greatly affected by quantum effects, but the translational kinetic energy is only slightly modified. The potential energy is also noticeably higher than in classical simulations. Finally, as a concluding remark, we have calcd. the formation energies of water clusters using both models, finding that the formation energies predicted by the rigid TIP4PQ/2005 model are lower by roughly 0.6 kcal/mol than those of the flexible q-TIP4P/F model for clusters of moderate size, the origin of this difference coming mainly from the geometrical distortion of the water mol. in the clusters that causes an increase in the intramol. potential energy.
- 36stlaPblog: a blog about Mathematics, R, Statistics. Rotation in Spherical Coordinates , 2016 https://stla.github.io/stlapblog/posts/RotationSphericalCoordinates.html. accessed 2024 April 29.There is no corresponding record for this reference.
- 37Miller Iii, T. F.; Eleftheriou, M.; Pattnaik, P.; Ndirango, A.; Newns, D.; Martyna, G. J. Symplectic Quaternion Scheme for Biophysical Molecular Dynamics. J. Chem. Phys. 2002, 116 (20), 8649– 8659, DOI: 10.1063/1.1473654There is no corresponding record for this reference.
- 38Weigend, F.; Ahlrichs, R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297– 3305, DOI: 10.1039/b508541a38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXpsFWgu7o%253D&md5=a820fb6055c993b50c405ba0fc62b194Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracyWeigend, Florian; Ahlrichs, ReinhartPhysical Chemistry Chemical Physics (2005), 7 (18), 3297-3305CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 mols. representing (nearly) all elements-except lanthanides-in their common oxidn. states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, d. functional theory and correlated methods, for which we had chosen Moller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.
- 39Bursch, M.; Mewes, J.-M.; Hansen, A.; Grimme, S. Best-practice DFT Protocols for Basic Molecular Computational Chemistry. Angew. Chem., Int. Ed. 2022, 61, e202205735 DOI: 10.1002/anie.20220573539https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xitl2kt7%252FO&md5=c562b2bd16bea8edc1ae18ad65216ce2Best-Practice DFT Protocols for Basic Molecular Computational ChemistryBursch, Markus; Mewes, Jan-Michael; Hansen, Andreas; Grimme, StefanAngewandte Chemie, International Edition (2022), 61 (42), e202205735CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Nowadays, many chem. investigations are supported by routine calcns. of mol. structures, reaction energies, barrier heights, and spectroscopic properties. The lion's share of these quantum-chem. calcns. applies d. functional theory (DFT) evaluated in at.-orbital basis sets. This work provides best-practice guidance on the numerous methodol. and tech. aspects of DFT calcns. in three parts: Firstly, we set the stage and introduce a step-by-step decision tree to choose a computational protocol that models the expt. as closely as possible. Secondly, we present a recommendation matrix to guide the choice of functional and basis set depending on the task at hand. A particular focus is on achieving an optimal balance between accuracy, robustness, and efficiency through multi-level approaches. Finally, we discuss selected representative examples to illustrate the recommended protocols and the effect of methodol. choices.
- 40Mardirossian, N.; Head-Gordon, M. ωB97M-V: A Combinatorially Optimized, Range-Separated Hybrid, Meta-GGA Density Functional with VV10 Nonlocal Correlation. J. Chem. Phys. 2016, 144, 214110, DOI: 10.1063/1.495264740https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XpsF2lt78%253D&md5=785288128d893d3914f3326f374b96d4ωB97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlationMardirossian, Narbe; Head-Gordon, MartinJournal of Chemical Physics (2016), 144 (21), 214110/1-214110/23CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A combinatorially optimized, range-sepd. hybrid, meta-GGA d. functional with VV10 nonlocal correlation is presented. The final 12-parameter functional form is selected from approx. 10 × 109 candidate fits that are trained on a training set of 870 data points and tested on a primary test set of 2964 data points. The resulting d. functional, ωB97M-V, is further tested for transferability on a secondary test set of 1152 data points. For comparison, ωB97M-V is benchmarked against 11 leading d. functionals including M06-2X, ωB97X-D, M08-HX, M11, ωM05-D, ωB97X-V, and MN15. Encouragingly, the overall performance of ωB97M-V on nearly 5000 data points clearly surpasses that of all of the tested d. functionals. In order to facilitate the use of ωB97M-V, its basis set dependence and integration grid sensitivity are thoroughly assessed, and recommendations that take into account both efficiency and accuracy are provided. (c) 2016 American Institute of Physics.
- 41Zhao, Y.; Truhlar, D. G. The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Functionals. Theor. Chem. Acc. 2008, 120, 215– 241, DOI: 10.1007/s00214-007-0310-x41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXltFyltbY%253D&md5=c31d6f319d7c7a45aa9b716220e4a422The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionalsZhao, Yan; Truhlar, Donald G.Theoretical Chemistry Accounts (2008), 120 (1-3), 215-241CODEN: TCACFW; ISSN:1432-881X. (Springer GmbH)We present two new hybrid meta exchange-correlation functionals, called M06 and M06-2X. The M06 functional is parametrized including both transition metals and nonmetals, whereas the M06-2X functional is a high-nonlocality functional with double the amt. of nonlocal exchange (2X), and it is parametrized only for nonmetals. The functionals, along with the previously published M06-L local functional and the M06-HF full-Hartree-Fock functionals, constitute the M06 suite of complementary functionals. We assess these four functionals by comparing their performance to that of 12 other functionals and Hartree-Fock theory for 403 energetic data in 29 diverse databases, including ten databases for thermochem., four databases for kinetics, eight databases for noncovalent interactions, three databases for transition metal bonding, one database for metal atom excitation energies, and three databases for mol. excitation energies. We also illustrate the performance of these 17 methods for three databases contg. 40 bond lengths and for databases contg. 38 vibrational frequencies and 15 vibrational zero point energies. We recommend the M06-2X functional for applications involving main-group thermochem., kinetics, noncovalent interactions, and electronic excitation energies to valence and Rydberg states. We recommend the M06 functional for application in organometallic and inorganometallic chem. and for noncovalent interactions.
- 42Peverati, R.; Truhlar, D. G. Screened-Exchange Density Functionals With Broad Accuracy for Chemistry and Solid-State Physics. Phys. Chem. Chem. Phys. 2012, 14, 16187– 16191, DOI: 10.1039/c2cp42576a42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xhs12jurbM&md5=c718c8b5a8e7aa2fc831216439b9ea31Screened-exchange density functionals with broad accuracy for chemistry and solid-state physicsPeverati, Roberto; Truhlar, Donald G.Physical Chemistry Chemical Physics (2012), 14 (47), 16187-16191CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)We present two new exchange-correlation functionals for hybrid Kohn-Sham electronic structure calcns. based on the nonseparable functional form introduced recently in the N12 and MN12-L functionals but now with the addn. of screened Hartree-Fock exchange. The 1st functional depends on the d. and the d. gradient and is called N12-SX; the 2nd functional depends on the d., the d. gradient, and the kinetic energy d. and is called MN12-SX. Both new functionals include a portion of the Hartree-Fock exchange at short-range, but Hartree-Fock exchange is screened at long range. The accuracies of the 2 new functionals are compared to those of the recent N12 and MN12-L local functionals to show the effect of adding screened exchange, are compared to the previously best available screened exchange functional, HSE06, and are compared to the best available global-hybrid generalized gradient approxn. (GGA) and to a high-performance long-range-cor. meta-GGA.
- 43Grimme, S.; Antony, J.; Ehrlich, S.; Krief, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132 (15), 154104, DOI: 10.1063/1.338234443https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXkvVyks7o%253D&md5=2bca89d904579d5565537a0820dc2ae8A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-PuGrimme, Stefan; Antony, Jens; Ehrlich, Stephan; Krieg, HelgeJournal of Chemical Physics (2010), 132 (15), 154104/1-154104/19CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The method of dispersion correction as an add-on to std. Kohn-Sham d. functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coeffs. and cutoff radii that are both computed from first principles. The coeffs. for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination nos. (CN). They are used to interpolate between dispersion coeffs. of atoms in different chem. environments. The method only requires adjustment of two global parameters for each d. functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of at. forces. Three-body nonadditivity terms are considered. The method has been assessed on std. benchmark sets for inter- and intramol. noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean abs. deviations for the S22 benchmark set of noncovalent interactions for 11 std. d. functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C6 coeffs. also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in mols. and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems. (c) 2010 American Institute of Physics.
- 44Mardirossian, N.; Head-Gordon, M. Thirty Years of Density Functional Theory in Computational Chemistry: an Overview and Extensive Assessment of 200 Density Functionals. Mol. Phys. 2017, 115 (19), 2315– 2372, DOI: 10.1080/00268976.2017.133364444https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVCltb3O&md5=ba27d707ee3f5fcdd949644d3d2cbd5eThirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionalsMardirossian, Narbe; Head-Gordon, MartinMolecular Physics (2017), 115 (19), 2315-2372CODEN: MOPHAM; ISSN:0026-8976. (Taylor & Francis Ltd.)In the past 30 years, Kohn-Sham d. functional theory has emerged as the most popular electronic structure method in computational chem. To assess the ever-increasing no. of approx. exchange-correlation functionals, this review benchmarks a total of 200 d. functionals on a mol. database (MGCDB84) of nearly 5000 data points. The database employed, provided as Supplemental Data, is comprised of 84 data-sets and contains non-covalent interactions, isomerisation energies, thermochem., and barrier heights. In addn., the evolution of non-empirical and semi-empirical d. functional design is reviewed, and guidelines are provided for the proper and effective use of d. functionals. The most promising functional considered is ωB97M-V, a range-sepd. hybrid meta-GGA with VV10 nonlocal correlation, designed using a combinatorial approach. From the local GGAs, B97-D3, revPBE-D3, and BLYP-D3 are recommended, while from the local meta-GGAs, B97M-rV is the leading choice, followed by MS1-D3 and M06-L-D3. The best hybrid GGAs are ωB97X-V, ωB97X-D3, and ωB97X-D, while useful hybrid meta-GGAs (besides ωB97M-V) include ωM05-D, M06-2X-D3, and MN15. Ultimately, today's state-of-the-art functionals are close to achieving the level of accuracy desired for a broad range of chem. applications, and the principal remaining limitations are assocd. with systems that exhibit significant self-interaction/delocalisation errors and/or strong correlation effects.
- 45Neese, F.; Wennmohs, F.; Becker, U.; Riplinger, C. The ORCA Quantum Chemistry Package. J. Chem. Phys. 2020, 152, 224– 108, DOI: 10.1063/5.0004608There is no corresponding record for this reference.
- 46Epifanovsky, E.; Gilbert, A. T. B.; Feng, X.; Lee, J.; Mao, Y.; Mardirossian, N.; Pokhilko, P.; White, A. F.; Coons, M. P.; Dempwolff, A. L.; Gan, Z. Software for the Frontiers of Quantum Chemistry: An Overview of Developments in the Q-Chem 5 package. J. Chem. Phys. 2021, 155 (8), 084801, DOI: 10.1063/5.005552246https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvVymsb3P&md5=34fdc0f501633082f75521c06be38ab2Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 packageEpifanovsky, Evgeny; Gilbert, Andrew T. B.; Feng, Xintian; Lee, Joonho; Mao, Yuezhi; Mardirossian, Narbe; Pokhilko, Pavel; White, Alec F.; Coons, Marc P.; Dempwolff, Adrian L.; Gan, Zhengting; Hait, Diptarka; Horn, Paul R.; Jacobson, Leif D.; Kaliman, Ilya; Kussmann, Jorg; Lange, Adrian W.; Lao, Ka Un; Levine, Daniel S.; Liu, Jie; McKenzie, Simon C.; Morrison, Adrian F.; Nanda, Kaushik D.; Plasser, Felix; Rehn, Dirk R.; Vidal, Marta L.; You, Zhi-Qiang; Zhu, Ying; Alam, Bushra; Albrecht, Benjamin J.; Aldossary, Abdulrahman; Alguire, Ethan; Andersen, Josefine H.; Athavale, Vishikh; Barton, Dennis; Begam, Khadiza; Behn, Andrew; Bellonzi, Nicole; Bernard, Yves A.; Berquist, Eric J.; Burton, Hugh G. A.; Carreras, Abel; Carter-Fenk, Kevin; Chakraborty, Romit; Chien, Alan D.; Closser, Kristina D.; Cofer-Shabica, Vale; Dasgupta, Saswata; de Wergifosse, Marc; Deng, Jia; Diedenhofen, Michael; Do, Hainam; Ehlert, Sebastian; Fang, Po-Tung; Fatehi, Shervin; Feng, Qingguo; Friedhoff, Triet; Gayvert, James; Ge, Qinghui; Gidofalvi, Gergely; Goldey, Matthew; Gomes, Joe; Gonzalez-Espinoza, Cristina E.; Gulania, Sahil; Gunina, Anastasia O.; Hanson-Heine, Magnus W. D.; Harbach, Phillip H. P.; Hauser, Andreas; Herbst, Michael F.; Hernandez Vera, Mario; Hodecker, Manuel; Holden, Zachary C.; Houck, Shannon; Huang, Xunkun; Hui, Kerwin; Huynh, Bang C.; Ivanov, Maxim; Jasz, Adam; Ji, Hyunjun; Jiang, Hanjie; Kaduk, Benjamin; Kahler, Sven; Khistyaev, Kirill; Kim, Jaehoon; Kis, Gergely; Klunzinger, Phil; Koczor-Benda, Zsuzsanna; Koh, Joong Hoon; Kosenkov, Dimitri; Koulias, Laura; Kowalczyk, Tim; Krauter, Caroline M.; Kue, Karl; Kunitsa, Alexander; Kus, Thomas; Ladjanszki, Istvan; Landau, Arie; Lawler, Keith V.; Lefrancois, Daniel; Lehtola, Susi; Li, Run R.; Li, Yi-Pei; Liang, Jiashu; Liebenthal, Marcus; Lin, Hung-Hsuan; Lin, You-Sheng; Liu, Fenglai; Liu, Kuan-Yu; Loipersberger, Matthias; Luenser, Arne; Manjanath, Aaditya; Manohar, Prashant; Mansoor, Erum; Manzer, Sam F.; Mao, Shan-Ping; Marenich, Aleksandr V.; Markovich, Thomas; Mason, Stephen; Maurer, Simon A.; McLaughlin, Peter F.; Menger, Maximilian F. S. J.; Mewes, Jan-Michael; Mewes, Stefanie A.; Morgante, Pierpaolo; Mullinax, J. Wayne; Oosterbaan, Katherine J.; Paran, Garrette; Paul, Alexander C.; Paul, Suranjan K.; Pavosevic, Fabijan; Pei, Zheng; Prager, Stefan; Proynov, Emil I.; Rak, Adam; Ramos-Cordoba, Eloy; Rana, Bhaskar; Rask, Alan E.; Rettig, Adam; Richard, Ryan M.; Rob, Fazle; Rossomme, Elliot; Scheele, Tarek; Scheurer, Maximilian; Schneider, Matthias; Sergueev, Nickolai; Sharada, Shaama M.; Skomorowski, Wojciech; Small, David W.; Stein, Christopher J.; Su, Yu-Chuan; Sundstrom, Eric J.; Tao, Zhen; Thirman, Jonathan; Tornai, Gabor J.; Tsuchimochi, Takashi; Tubman, Norm M.; Veccham, Srimukh Prasad; Vydrov, Oleg; Wenzel, Jan; Witte, Jon; Yamada, Atsushi; Yao, Kun; Yeganeh, Sina; Yost, Shane R.; Zech, Alexander; Zhang, Igor Ying; Zhang, Xing; Zhang, Yu; Zuev, Dmitry; Aspuru-Guzik, Alan; Bell, Alexis T.; Besley, Nicholas A.; Bravaya, Ksenia B.; Brooks, Bernard R.; Casanova, David; Chai, Jeng-Da; Coriani, Sonia; Cramer, Christopher J.; Cserey, Gyorgy; DePrince, A. Eugene; DiStasio, Robert A.; Dreuw, Andreas; Dunietz, Barry D.; Furlani, Thomas R.; Goddard, William A.; Hammes-Schiffer, Sharon; Head-Gordon, Teresa; Hehre, Warren J.; Hsu, Chao-Ping; Jagau, Thomas-C.; Jung, Yousung; Klamt, Andreas; Kong, Jing; Lambrecht, Daniel S.; Liang, WanZhen; Mayhall, Nicholas J.; McCurdy, C. William; Neaton, Jeffrey B.; Ochsenfeld, Christian; Parkhill, John A.; Peverati, Roberto; Rassolov, Vitaly A.; Shao, Yihan; Slipchenko, Lyudmila V.; Stauch, Tim; Steele, Ryan P.; Subotnik, Joseph E.; Thom, Alex J. W.; Tkatchenko, Alexandre; Truhlar, Donald G.; Van Voorhis, Troy; Wesolowski, Tomasz A.; Whaley, K. Birgitta; Woodcock, H. Lee; Zimmerman, Paul M.; Faraji, Shirin; Gill, Peter M. W.; Head-Gordon, Martin; Herbert, John M.; Krylov, Anna I.Journal of Chemical Physics (2021), 155 (8), 084801CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A review. This article summarizes tech. advances contained in the fifth major release of the Q-Chem quantum chem. program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced d.-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decompn. anal. techniques. High-performance capabilities including multithreaded parallelism and support for calcns. on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design. (c) 2021 American Institute of Physics.
- 47Smith, D. G. A.; Burns, L. A.; Simmonett, A. C.; Parrish, R. M.; Schieber, M. C.; Galvelis, R.; Kraus, P.; Kruse, H.; Di Remigio, R.; Alenaizan, A.; James, A. M. Psi4 1.4: Open-Source Software for High-Throughput Quantum Chemistry. J. Chem. Phys. 2020, 152 (18), 184108, DOI: 10.1063/5.000600247https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXps1Ogsrk%253D&md5=7aaec598ebcd0a728cd43bbba7559602PSI4 1.4: Open-source software for high-throughput quantum chemistrySmith, Daniel G. A.; Burns, Lori A.; Simmonett, Andrew C.; Parrish, Robert M.; Schieber, Matthew C.; Galvelis, Raimondas; Kraus, Peter; Kruse, Holger; Di Remigio, Roberto; Alenaizan, Asem; James, Andrew M.; Lehtola, Susi; Misiewicz, Jonathon P.; Scheurer, Maximilian; Shaw, Robert A.; Schriber, Jeffrey B.; Xie, Yi; Glick, Zachary L.; Sirianni, Dominic A.; O'Brien, Joseph Senan; Waldrop, Jonathan M.; Kumar, Ashutosh; Hohenstein, Edward G.; Pritchard, Benjamin P.; Brooks, Bernard R.; Schaefer, Henry F.; Sokolov, Alexander Yu.; Patkowski, Konrad; DePrince, A. Eugene; Bozkaya, Ugur; King, Rollin A.; Evangelista, Francesco A.; Turney, Justin M.; Crawford, T. Daniel; Sherrill, C. DavidJournal of Chemical Physics (2020), 152 (18), 184108CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)PSI4 is a free and open-source ab initio electronic structure program providing implementations of Hartree-Fock, d. functional theory, many-body perturbation theory, CI, d. cumulant theory, symmetry-adapted perturbation theory, and coupled-cluster theory. Most of the methods are quite efficient, thanks to d. fitting and multi-core parallelism. The program is a hybrid of C + + and Python, and calcns. may be run with very simple text files or using the Python API, facilitating post-processing and complex workflows; method developers also have access to most of PSI4's core functionalities via Python. Job specification may be passed using The Mol. Sciences Software Institute (MolSSI) QCSCHEMA data format, facilitating interoperability. A rewrite of our top-level computation driver, and concomitant adoption of the MolSSI QCARCHIVE INFRASTRUCTURE project, makes the latest version of PSI4 well suited to distributed computation of large nos. of independent tasks. The project has fostered the development of independent software components that may be reused in other quantum chem. programs. (c) 2020 American Institute of Physics.
- 48Helgaker, T.; Klopper, W.; Koch, H.; Noga Basis-set Convergence of Correlated Calculations on Water. J. Chem. Phys. 1997, 106, 9639– 9646, DOI: 10.1063/1.47386348https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXjvVCgu78%253D&md5=f4689c1b38fe30eb721e9cd7d607bdf7Basis-set convergence of correlated calculations on waterHelgaker, Trygve; Klopper, Wim; Koch, Henrik; Noga, JozefJournal of Chemical Physics (1997), 106 (23), 9639-9646CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The basis-set convergence of the electronic correlation energy in the water mol. is investigated at the second-order Moller-Plesset level and at the coupled-cluster singles-and-doubles level with and without perturbative triples corrections applied. The basis-set limits of the correlation energy are established to within 2mEh by means of (1) extrapolations from sequences of calcns. using correlation-consistent basis sets and (2) from explicitly correlated calcns. employing terms linear in the inter-electronic distances rij. For the extrapolations to the basis-set limit of the correlation energies, fits of the form a + bX-3 (where X is two for double-zeta sets, three for triple-zeta sets, etc.) are found to be useful. CCSD(T) calcns. involving as many as 492 AOs are reported.
- 49Vasilyev, V. Online Complete Basis Set Limit Extrapolation Calculator. Comp. Theor. Chem. 2017, 1115, 1– 3, DOI: 10.1016/j.comptc.2017.06.001There is no corresponding record for this reference.
- 50Welch, B. K.; Almeida, N. M. S.; Wilson, A. K. Super-ccCA (s-ccCA): An Approach for Accurate Transition Metal Chemistry. Mol. Phys. 2021, 119, e1963001 DOI: 10.1080/00268976.2021.1963001There is no corresponding record for this reference.
- 51Kreisle, D.; Echt, O.; Knapp, M.; Recknagel, E. Evolution of “Magic Numbers” in Mass Spectra of Clusters After Ionization. Surf. Sci. 1985, 156 (1), 321– 327, DOI: 10.1016/0039-6028(85)90590-4There is no corresponding record for this reference.
- 52Matro, A.; Freeman, D. L.; Topper, R. Q. Computational Study of the Structures and Thermodynamic Properties of Ammonium Chloride Clusters Using a Parallel Jump-Walking Approach. J. Chem. Phys. 1996, 104, 8690– 8702, DOI: 10.1063/1.47155852https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28Xjt1OhsL0%253D&md5=24f03a4187cc6a0370eadd64af66114cComputational study of the structures and thermodynamic properties of ammonium chloride clusters using a parallel jump-walking approachMatro, Alexander; Freeman, David L.; Topper, Robert Q.Journal of Chemical Physics (1996), 104 (21), 8690-8702CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The thermodn. and structural properties of (NH4Cl)n clusters, n = 3-10 are studied. Using the method of simulated annealing, the geometries of several isomers for each cluster size are examd. Jump-walking Monte Carlo simulations are then used to compute the const.-vol. heat capacity for each cluster size over a wide temp. range. To carry out these simulations a new parallel algorithm is developed using the parallel virtual machine (PVM) software package. Features of the cluster potential energy surfaces, such as energy differences among isomers and rotational barriers of the ammonium ions, are found to play important roles in detg. the shape of the heat capacity curves.
- 53Tao, F.-M. Direct Formation of Solid Ammonium Chloride Particles From HCl and NH3 Vapors. J. Chem. Phys. 1999, 110, 11121– 11124, DOI: 10.1063/1.479054There is no corresponding record for this reference.
- 54Biswakarma, J. J.; Ciocoi, V.; Topper, R. Q. Energetics Thermodynamics, and Hydrogen Bonding Diversity in Ammonium Halide Clusters. J. Phys. Chem. A 2016, 120, 7924– 7934, DOI: 10.1021/acs.jpca.6b0678854https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFGrs7rI&md5=b90f5c92202633b8daa65f240c97af81Energetics, Thermodynamics, and Hydrogen Bonding Diversity in Ammonium Halide ClustersBiswakarma, John J.; Ciocoi, Vlad; Topper, Robert Q.Journal of Physical Chemistry A (2016), 120 (40), 7924-7934CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)Contributions from different intermol. and interionic forces, as well as variations in bond energies, produce size-dependent variations in the structures of acid-base mol. clusters. In this work the structures and interaction energetics of cluster particles with the nominal formulas (NH4X)n, X = (F, Cl, Br) are predicted using either "mag-walking" sawtooth simulated annealing Monte Carlo calcns. or model building, followed by M06-2X or RI-MP2 geometry optimization and single-point energy calcns. Whereas the n = 1 clusters all exhibit a single hydrogen bond, small (NH4F)n particles (n = 2-5) exhibit three distinct types of hydrogen bonds as a function of size (traditional, ion-pair and proton-shared). However, (NH4Br)n and (NH4Cl)n particles (n = 2-13) all solely exhibit ion-pair hydrogen bonding, with even values of n exhibiting pronounced relative stability. The computed differential interaction energy of the bromide and chloride systems is generally near the bulk limit of the difference in their accepted lattice energies, despite the fact that their structures do not resemble the bulk crystal structures. Nanoparticle growth reactions are predicted to be thermodynamically spontaneous under std. conditions, with significant size and system dependencies. This work is designed to further our understanding of the nature of hydrogen bonding and other intermol. forces, particularly within ionic nanocrystallites, as well as the thermodn. of cluster formation.
- 55Hendricks, S. B.; Posnjak, E.; Kracek, F. C. Molecular Rotation in the Solid State. The Variation of the Crystal Structure of Ammonium Nitrate with Temperature. J. Am. Chem. Soc. 1932, 54 (7), 2766– 2786, DOI: 10.1021/ja01346a020There is no corresponding record for this reference.
- 56Rapoport, E.; Pistorius, C. W. F. T. Polymorphism and Melting of Ammonium, Thallous, and Silver Nitrates to 45 kbar. J. Chem. Phys. 1966, 44, 1514– 1519, DOI: 10.1063/1.172688756https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF28XlsF2itQ%253D%253D&md5=0e8bf0792a931131d8e7d172a43123daPolymorphism and melting of ammonium, thallous, and silver nitrates to 45 kilobarsRapoport, Eliezer; Pistorius, Carl W. F. T.Journal of Chemical Physics (1966), 44 (4), 1514-19CODEN: JCPSA6; ISSN:0021-9606.The phase diagrams of NH4NO3 and TlNO3 were detd. by means of differential thermal analysis (DTA) to 40 kilobars. The NH4NO3 I/VI, IV/VI, and I/IV transition lines meet at a triple point near 19.5 kilobars and 256°. The TlNO3 I/II transition line can be represented by t (degrees C.) = 144.6 +7.91P- 0.062P2, and the melting curve of TlNO3 I is given by P (kilobars) = 5.00 [(T/479)3.531 -1]. The phase diagram of AgNO3 was detd. by means of DTA and volumetric methods to 45 kilobars. In addn. to the 4 phases previously known, metastable AgNO3 V can be obtained by suitable manipulation above 21 kilobars at <50°. The metastable AgNO3 I/V transition is easily reversible. AgNO3 V reverts to stable AgNO3 II if left under pressure overnight. The melting curve of AgNO3 II is given by P (kilobars) = 0.17[(T/ 483)4.438-1].
- 57Chellappa, R. S.; Dattelbaum, D. M.; Velisavljevic, N.; Sheffield, S. The Phase Diagram of Ammonium Nitrate. J. Chem. Phys. 2012, 137 (2012), 064504, DOI: 10.1063/1.4733330There is no corresponding record for this reference.
- 58Kaniewski, M.; Huculak-Maczka, M.; Zielinski, J.; Biegun, M.; Hoffmann, K.; Hoffmann, J. Crystalline Phase Transitions and Reactivity of Ammonium Nitrate in Systems Containing Selected Carbonate Salts. Crystals 2021, 11 (10), 1250, DOI: 10.3390/cryst11101250There is no corresponding record for this reference.
- 59Lomboy, A. J. A Computational Study of Solvation Effects on Ammonium Nitrate Clusters M.Eng. Dissertation; The Cooper Union for the Advancement of Science and Art, New York, NY, 2020.There is no corresponding record for this reference.
- 60Fárník, M. Bridging Gaps between Clusters in Molecular Beam Experiments and Aerosol Nanoclusters. J. Phys. Chem. Lett. 2023, 14 (1), 287– 294, DOI: 10.1021/acs.jpclett.2c03417There is no corresponding record for this reference.
- 61Kubečka, J.; Besel, V.; Neefjes, I.; Knattrup, Y.; Kurtén, T.; Vehkamäki, H.; Elm, J. Computational Tools for Handling Molecular Clusters: Configurational Sampling, Storage, Analysis, and Machine Learning. ACS Omega 2023, 8 (47), 45115– 45128, DOI: 10.1021/acsomega.3c07412There is no corresponding record for this reference.
- 62Hanwell, M. D.; Curtis, D. E.; Lonie, D. C.; Vandermeersch, T.; Zuek, E.; Hutchison, G. R. Avogadro: An Advanced Semantic Chemical Editor, Visualization, and Analysis Platform. J. Cheminf. 2012, 4 (1), 17, DOI: 10.1186/1758-2946-4-1762https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVGksLg%253D&md5=f10400f51db314afa780e99403ca748aAvogadro: an advanced semantic chemical editor, visualization, and analysis platformHanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.; Vandermeersch, Tim; Zurek, Eva; Hutchison, Geoffrey R.Journal of Cheminformatics (2012), 4 (), 17CODEN: JCOHB3; ISSN:1758-2946. (Chemistry Central Ltd.)Background: The Avogadro project has developed an advanced mol. editor and visualizer designed for cross-platform use in computational chem., mol. modeling, bioinformatics, materials science, and related areas. It offers flexible, high quality rendering, and a powerful plugin architecture. Typical uses include building mol. structures, formatting input files, and analyzing output of a wide variety of computational chem. packages. By using the CML file format as its native document type, Avogadro seeks to enhance the semantic accessibility of chem. data types. Results: The work presented here details the Avogadro library, which is a framework providing a code library and application programming interface (API) with three-dimensional visualization capabilities; and has direct applications to research and education in the fields of chem., physics, materials science, and biol. The Avogadro application provides a rich graphical interface using dynamically loaded plugins through the library itself. The application and library can each be extended by implementing a plugin module in C++ or Python to explore different visualization techniques, build/manipulate mol. structures, and interact with other programs. We describe some example extensions, one which uses a genetic algorithm to find stable crystal structures, and one which interfaces with the PackMol program to create packed, solvated structures for mol. dynamics simulations. The 1.0 release series of Avogadro is the main focus of the results discussed here. Conclusions: Avogadro offers a semantic chem. builder and platform for visualization and anal. For users, it offers an easy-to-use builder, integrated support for downloading from common databases such as PubChem and the Protein Data Bank, extg. chem. data from a wide variety of formats, including computational chem. output, and native, semantic support for the CML file format. For developers, it can be easily extended via a powerful plugin mechanism to support new features in org. chem., inorg. complexes, drug design, materials, biomols., and simulations.
- 63Spartan 24 version 1.2.0; Wavefunction, Inc.: Irvine, CA, USA, 2024. https://www.wavefun.com/. accessed 2024 July 09.There is no corresponding record for this reference.
- 64TransRot version 1.6.4; The Cooper Union for the Advancement of Science and Art: New York, NY, USA,2024. https://github.com/steventopper/TransRot. accessed 2024 July 09.There is no corresponding record for this reference.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.4c04630.
Detailed description of optimization parameters. OPLS-AA parameters used in the simulated annealing calculations are provided. Computed interaction energies of (neutral) nanoparticles and cation and anion clusters. The computed energies of all species presented in this work. The coordinates in XYZ format for all ωB97X-D3/def2-SVPD optimized cation and anion clusters and nanoparticles. The optimized OPLS-AA and ωB97X-D3/6-31G(d) structures in XYZ format for the nanoparticles presented in this work (PDF)
Structures of ammonium nitrate(ZIP)
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