The role of thermodynamics in assessing the intrinsic instability of the CH₃NH₃PbX₃ perovskites (X = Cl,Br,I) is outlined on the basis of the available experimental information. Possible decomposition/degradation pathways driven by the inherent instability of the material are considered. The decomposition to precursors CH₃NH₃X(s) and PbX₂(s) is first analyzed, pointing out the importance of both the enthalpic and the entropic factor, the latter playing a stabilizing role making the stability higher than often asserted. For CH₃NH₃PbI₃, the disagreement between the available calorimetric results makes the stability prediction uncertain. Subsequently, the gas-releasing decomposition paths are discussed, with emphasis on the discrepant results presently available, probably reflecting the predominance of thermodynamic or kinetic control. The competition between the formation of NH₃(g) + CH₃X(g), CH₃NH₂(g) + HX(g) or CH₃NH₃X(g) is analyzed, in comparison with the thermal decomposition of methylammonium halides. In view of the scarce and inconclusive thermodynamic studies to-date available, the need for further experimental data is emphasized.

Photovoltaic (PV) device development is much more expensive and time-consuming than the development of the absorber layer alone. This Perspective focuses on two methods that can be used to rapidly assess and develop PV absorber materials independent of device development. The absorber material properties of quasi-Fermi level splitting and carrier diffusion length under steady effective 1 Sun illumination are indicators of a material’s ability to achieve high V_OC and J_SC. These two material properties can be rapidly and simultaneously assessed with steady-state absolute intensity photoluminescence and photoconductivity measurements. As a result, these methods are extremely useful for predicting the quality and stability of PV materials prior to PV device development. Here, we summarize the methods, discuss their strengths and weaknesses, and compare photoluminescence and photoconductivity results with device performance for four hybrid perovskite compositions of various bandgaps (1.35–1.82 eV), CISe, CIGSe, and CZTSe.

We investigate reactions between laser-cooled Be⁺ ions and room-temperature water molecules using an integrated ion trap and high-resolution time-of-flight mass spectrometer. This system allows simultaneous measurement of individual reaction rates that are resolved by reaction product. The rate coefficient of the Be⁺(²S_1/2) + H₂O → BeOH⁺ + H reaction is measured for the first time and is found to be approximately two times smaller than predicted by an ion–dipole capture model. Zero-point-corrected quasi-classical trajectory calculations on a highly accurate potential energy surface for the ground electronic state reveal that the reaction is capture-dominated, but a submerged barrier in the product channel lowers the reactivity. Furthermore, laser excitation of the ions from the ²S_1/2 ground state to the ²P_3/2 state opens new reaction channels, and we report the rate and branching ratio of the Be⁺(²P_3/2) + H₂O → BeOH⁺ + H and H₂O⁺ + Be reactions. The excited-state reactions are nonadiabatic in nature.

We describe a two-color, isotopomer-selective infrared–infrared population-labeling method that can monitor very slow spectral diffusion of OH oscillators in H-bonded networks and apply it to the I^–·(HDO)·(D₂O) and I^–·(H₂O)·(D₂O) systems, which are cryogenically cooled and D₂-tagged at an ion trap temperature of 15 K. These measurements reveal very large (>400 cm^–1), spontaneous spectral shifts despite the fact that the predissociation spectra in the OH stretching region of both isotopologues are sharp and readily assigned to four fundamentals of largely decoupled OH oscillators held in a cyclic H-bonded network. This spectral diffusion is not observed in the untagged isotopologues of the dihydrate clusters that are generated under the same source conditions but does become apparent at about 75 K. These results are discussed in the context of the large-amplitude “jump” mechanism for H-bond relaxation dynamics advanced by Laage and Hynes in an experimental scenario where rare events can be captured by following the migration of OH groups among the four available positions in the quasi-rigid equilibrium structure.

Besides the use as cold matrix for spectroscopic studies, superfluid helium droplets have served as a cold environment for the synthesis of molecules and clusters. Since vibrational frequencies of molecules in helium droplets exhibit almost no shift compared to the free molecule values, one could assume the solvated particles move frictionless and undergo a reaction as soon as their paths cross. There have been a few unexplained observations that seemed to indicate cases of two species on one droplet not forming bonds but remaining isolated. In this work, we performed a systematic study of helium droplets doped with one rubidium and one strontium atom showing that besides a reaction to RbSr, there is a probability of finding separated Rb and Sr atoms on one droplet that only react after electronic excitation. Our results further indicate that ground-state Sr atoms can reside at the surface as well as inside the droplet.

We report an investigation of lead halide perovskite CH₃NH₃PbBr₃ nanocrystals and associated ligand molecules by combining several different state-of-the-art experimental techniques, including synchrotron radiation-based XPS and VUV PES of free-standing nanocrystals isolated in vacuum. By using this novel approach for perovskite materials, we could directly obtain complete band alignment to vacuum of both CH₃NH₃PbBr₃ nanocrystals and the ligands widely used in their preparation. We discuss the possible influence of the ligand molecules to apparent perovskite properties, and we compare the electronic properties of nanocrystals to those of bulk material. The experimental results were supported by DFT calculations.

The magnetic compass sense utilized by migratory birds for long-distance navigation functions only once light of a certain wavelength is present. This piece of evidence fits partially with the popular hypothesis of chemical magnetoreception in cryptochrome proteins, located in the bird retina. According to this hypothesis a magnetosensitive radical pair is produced after photoexcitation of an FAD cofactor inside cryptochrome, and as such the absorption properties of FAD are of crucial importance for cryptochrome activation. However, we reveal that absorption spectra of FAD show very little variation between six different cryptochromes, suggesting that the electronic transitions are barely affected by the chemical differences in the proteins. This conclusion hints on the presence of a secondary photoreceptor or cofactor that could be necessary to explain green-light-activated magnetoreception in birds.

Molecular photonic wires (MPWs) are tunable nanophotonic structures capable of capturing and directing light with high transfer efficiencies. DNA-based assembly techniques provide a simple and economical preparation method for MPWs that allows precise positioning of the molecular transfer components. Unfortunately, the longest DNA-based MPWs (∼30 nm) report only modest transfer efficiencies of ∼2% and have not been demonstrated on solid-state platforms. Here, we demonstrate that DNA-based MPWs can be spin-coated in a polymer matrix onto silicon wafers and exhibit a 5-fold increase in photonic transfer efficiency over solution-phase MPWs. Cooling these MPWs to 5 K led to further efficiency increases ranging from ∼40 to 240% depending on the length of the MPW. The improvement of MPW energy transport efficiencies advances prospects for their incorporation in a variety of optoelectronics technologies and makes them an ideal test bed for further exploration of nanoscale energy transfer.

A highly potent donor–acceptor biaryl thermally activated delayed fluorescence (TADF) dye is accessible by a concise two-step sequence employing two-fold Ullmann arylation and a sequentially Pd-catalyzed Masuda borylation–Suzuki arylation (MBSA). Photophysical investigations show efficient TADF at ambient temperature due to the sterical hindrance between the donor and acceptor moieties. The photoluminescence quantum yield amounts to Φ_PL = 80% in toluene and 90% in PMMA arising from prompt and delayed fluorescence with decay times of 21 ns and 30 μs, respectively. From an Arrhenius plot, the energy gap ΔE(S₁ – T₁) between the lowest excited singlet S₁ and triplet T₁ state was determined to be 980 cm^–1 (120 meV). A new procedure is proposed that allows us to estimate the intersystem crossing time to ∼10² ns.

We derive a theoretical expression of the second harmonic scattering signal in diluted electrolytes compared with bulk water. We show that the enhancement of the signal with respect to pure water observed recently for electrolytes at very low dilution in the micromolar range is a mere manifestation of the Debye screening that makes the infinite-range dipole–dipole solvent correlations in 1/r³ disappear as soon as the ionic concentration becomes finite. In q space, this translates into a correlation function having a well known singular behavior around q = 0, which drives the observed ionic effects. We find that the signal is independent of the ion-induced long-range behavior of the function ⟨cos ϕ(r)⟩ that has been recently discussed. We find also that the enhancement depends on the experimental geometry and occurs only for in-plane polarization detection, as observed experimentally. On the contrary, the measured isotope effect between light and heavy water cannot be fully explained.

NMR spectroscopy is one of the most useful methods for detection and characterization of hydrogen bond (H-bond) interactions in biological systems. For H bonds X–H···Y, where X and Y are O or N, it is generally believed that a decrease in ¹H-shielding constants relates to a shortening of H-bond donor–acceptor distance. Here we investigated computationally the trend of ¹H-shielding constants for hydrogen-bonded protons in a series of guanine C8-substituted GC pair model compounds as a function of the molecular structure. Furthermore, the electron density distribution around the hydrogen atom was analyzed with the Voronoi deformation density (VDD) method. Our findings demonstrate that ¹H-shielding values of the hydrogen bond are determined by the depletion of charge around the hydrogen atom, which stems from the fact that electrons obey the Pauli exclusion principle.

The three-electron two-center (3e–2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e–2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e–2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e–2c-bound CH₃S∴S(H)CH₃ and the strongly 3e–2c-bound (CH₃SH)₂⁺ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH₃S∴S(H)CH₃ to form [CH₃(H)S∴S(H)CH₃]⁺ significantly enhances the 3e–2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S–S distance from 3.00 to 2.86 Å, and a dissociation energy increased from ∼23 to 162 kJ mol^–1.

Molecular polaritons have gained considerable attention due to their potential to control nanoscale molecular processes by harnessing electromagnetic coherence. Although recent experiments with liquid-phase vibrational polaritons have shown great promise for exploiting these effects, significant challenges remain in interpreting their spectroscopic signatures. We develop a quantum-mechanical theory of pump–probe spectroscopy for this class of polaritons based on the quantum Langevin equation and the input–output theory. Comparison with recent experimental data shows good agreement upon consideration of the various vibrational anharmonicities that modulate the signals. Finally, a simple and intuitive interpretation of the data based on an effective mode-coupling theory is provided. Our work provides a solid theoretical framework to elucidate nonlinear optical properties of molecular polaritons as well as to analyze further multidimensional spectroscopy experiments on these systems.

Neutron diffraction experiments have been performed to investigate and compare the structure of the hydration shell of three monosaccharides, namely, fructose, glucose, and mannose. It is found that despite their differences with respect to many thermodynamical quantities, bioprotective properties against environmental stresses, and taste, the influence of these monosaccharides on the bulk water solvent structure is virtually identical. Conversely, these sugars interact with the neighboring water molecules by forming H bonds of different length and strength. Interestingly, the sweetness of these monosaccharides, along with that of the disaccharide trehalose, is correlated with the length of these H bonds. This suggests that the small differences in stereochemistry between the different sugars determine a relevant change in polarity, which has a fundamental impact on the behavior of these molecules in vivo.

We report on a comprehensive measurement system for mobility and energy states of charge carriers in matter under dynamic chemical doping. The temporal evolution of the iodine doping process of poly(3-hexylthiophene) (P3HT) was monitored directly through electron paramagnetic resonance (EPR) and optical absorption spectroscopy, as well as differential electrical conductivity by the microwave conductivity measurement. The increase in conductivity was observed after the EPR intensity reached a maximum and declined thereafter, and the conductivity finally reached ∼80 S cm^–1. The carrier species changed from a paramagnetic polaron with an estimated mobility of μ_P+ ≈ 2 × 10^–3 cm² V^–1 s^–1 to an antiferromagnetic polaron pair with μ_PP+ ≈ 0.6 cm² V^–1 s^–1. The technique presented here can be a ubiquitous method for rapid and direct observation of charge carrier mobility and energy states in p-type semiconducting materials as a completely noncontact, experimental, and quantitative technique.

Responding to changes in the surrounding environment, aerosol particles can grow by water condensation changing rapidly in composition and changing dramatically in viscosity. The timescale for growth is important to establish for particles undergoing hydration processes in the atmosphere or during inhalation. Using an electrodynamic balance, we report direct measurements at −7.5, 0, and 20 °C of timescales for hygroscopic condensational growth on a range of model hygroscopic aerosol systems. These extend from viscous aerosol particles containing a single saccharide solute (sucrose, glucose, raffinose, or trehalose) and a starting viscosity equivalent to a glass of ∼10¹² Pa·s, to nonviscous (∼10^–2 Pa·s) tetraethylene glycol particles. The condensation timescales observed in this work indicate that water condensation occurs rapidly at all temperatures examined (<10 s) and for particles of all initial viscosities spanning 10^–2 to 10¹² Pa·s. Only a marginal delay (<1 order of magnitude) is observed for particles starting as a glass.

The photophysical properties of a series of heteroatom substituted indoles are explored to identify chemical means to control their emissive activity. In particular, we consider impacts of changes in the conjugated backbone, where the C═N bonds of benzoxazoles are replaced by C═P bonds (benzoxaphospholes). The effects of extending the π-conjugation, incorporating various secondary heteroatoms (X–C═P), and enforcing planar rigidity are also examined. Our computational analysis explains the higher fluorescence efficiency observed with extended π-conjugation and highlights the importance of maintaining molecular planarity at both ground- and emissive-state geometries.

This work is pioneering to introduce molecular electrostatic potential (MESP) to investigate the interaction between lithium ions and organic electrode molecules. The electrostatic potential on the van der Waals surface of the electrode molecule is calculated, and then the coordinates and relative values of the local minima of MESP can be correlated to the Li binding sites and sequence on an organic small molecule, respectively. This suggests a gradual lithiation process. Similar calculations are extended to polymers and even organic crystals. The operation process of MESP for these systems is explained in detail. Through providing accurate and visualizable lithium binding sites, MESP can give precise prediction of the lithiated structures and reaction mechanism of organic electrode materials. It will become a new theoretical tool for determining the feasibility of organic electrode materials for alkali metal ion batteries.

Detailed understanding of the current-induced fluorescence mechanism constitutes an exciting challenge as it can open the way to efficient coupling between an electric field and light at the nanoscale. At the same time, a number of published experimental studies give an unclear, contradictory picture of this phenomenon working principle. Here, for a system consisting of a silver tip and a porphyrin molecule, we perform for the first time fully atomistic, real-time nonadiabatic dynamics simulations to study the process of energy transfer and relaxation in an STM setup. We calculate time scales of all crucial processes and explain their atomic details. On this basis, we confirm and characterize the dual mechanism of the observed emission based on competing elastic and inelastic electron transfer between the metal tip and the molecule.

Lead selenide (PbSe) colloidal quantum dots (CQDs) are considered to be a strong candidate for high-efficiency colloidal quantum dot solar cells (CQDSCs) due to its efficient multiple exciton generation. However, currently, even the best PbSe CQDSCs can only display open-circuit voltage (V_oc) about 0.530 V. Here, we introduce a solution-phase ligand exchange method to prepare PbI₂-capped PbSe (PbSe-PbI₂) CQD inks, and for the first time, the absorber layer of PbSe CQDSCs was deposited in one step by using this PbSe-PbI₂ CQD inks. One-step-deposited PbSe CQDs absorber layer exhibits fast charge transfer rate, reduced energy funneling, and low trap assisted recombination. The champion large-area (active area is 0.35 cm²) PbSe CQDSCs fabricated with one-step PbSe CQDs achieve a power conversion efficiency (PCE) of 6.0% and a V_oc of 0.616 V, which is the highest V_oc among PbSe CQDSCs reported to date.

Inorganic halide perovskites exhibit significant photovoltaic performance due to their structural stability and high open-circuit voltage (V_oc). Herein, a general strategy of solution engineering has been implemented to enable a wide solution-processing window for high V_oc (∼1.3 V) and power conversion efficiency (PCE, ∼12.5%). We introduce a nontoxic solvent of dimethyl sulfoxide (DMSO) and an assisted heating process in the fabrication of CsPbI₂Br (CPI2) to control the improved crystallization. A wide solution-processing window including a wide range of solvent components and solute concentrations has been realized. The CPI2-based inorganic perovskite solar cells (IPSCs) exhibit a high PCE up to 12.52%. More importantly, these devices demonstrate a remarkable V_oc of 1.315 V. The performance has possessed such a region with high V_oc and PCE in all Cs-based IPSCs, unveiling wide solution-processing windows with enhanced solution processability facilitating potential industrial application especially for tandem solar cells.

Defect engineering is promising for tailoring the properties of atomically thin materials. By creating defects via Se vacancies, we study the optoelectronic properties of monolayer PbSe. We obtain the single-particle properties using the density functional theory plus a first-principles-based typical medium approximation. The absorption spectra are explored by solving the Bethe–Salpeter equation. Our results reveal that monolayer PbSe is defect-sensitive but defect-tolerant. The latter fingerprint is due to the absence of defect-induced in-gap, localized states. Our results predict that Se vacancies are the dominant defect type in disordered PbSe monolayer. We observe that increasing Se vacancy concentrations δ renormalize the energy bandgap E_g, which increased from 0.21 eV for the pristine to as high as 0.45 eV at high δ. The high tunability of the optoelectronic properties of monolayer PbSe using defect-engineering makes this material a candidate for exploring flexible electronic with potential technological applications in nanoelectronics.

A novel methodology is reported on the use of internally referenced diffusion-ordered spectroscopy (IR-DOSY) in divulging the solution structure of lithium-ion battery electrolytes. Toluene was utilized as the internal reference for ¹H-DOSY analysis due to its exceptionally low donor number and reasonable solubility in various electrolytes. With the introduction of the internal reference, the solvent coordination ratio of different species in the electrolytes can be easily determined by ¹H-DOSY or ⁷Li-DOSY. This new technique was applied to different carbonate electrolytes, and the results were consistent with a Fourier transform infrared (FTIR) analysis. Compared to conventional vibrational spectroscopy, this IR-DOSY technique avoids the complicated deconvolution of the spectrum and allows determination of the solvent coordination ratio of different species in electrolyte systems with two or more organic solvents.

Lithium sulfur batteries promise significant improvements in specific energy compared to Li-ion, but are limited by capacity fade upon cycling. Efforts to improve durability have focused on suppressing the solubility of intermediate polysulfides in the electrolyte. Here we describe an in situ electrochemical polysulfide detection method based on the cyclic volatmmetric response. The voltammetric peaks correlate with increased discharge, consistent with increased polysulfide species in the electrolyte as demonstrated by prior literature measurements using spectroscopic methods. We verified that adding metal sulfide species to the sulfur cathode and ceramic-coatings on the polyolefin separator result in reduced polysulfide concentration, consistent with improved cycle life reported earlier. Further, the use of highly concentrated electrolytes produces no detectable dissolved polysulfide species. Future advances in Li/S technology could utilize this method to determine the polysulfide contents in the electrolyte, and thus quantify the efficacy of the sulfur-sequestering strategies.

The presence of active metal nanoparticles on the surface significantly increases the electrochemical performance of ABO₃ perovskite oxide materials. While conventional deposition methods can improve the activity, in situ exsolution produces nanoparticles with far greater stability. The migration of transition metal atoms toward the surface is expected to affect the exsolution process. To study the energetics, we use ab initio computations combined with experiments in a SrTiO₃-based model system. Our calculations show that Ni preferentially segregates toward the (100)-oriented and SrTiO-terminated surfaces, note that this orientation is identical to one reported by the Irvine and Gorte groups. Vacancies in the Sr-site and O-site promote the segregation of Ni, while placing La on the Sr-site has an opposite effect. The corresponding experiments are in agreement with the computational predictions. Fast nanoparticle growth and activity enhancement are found in STO system with Sr vacancies and without La. The approach developed in this Letter could be used to study the mechanism of exsolution in other material systems, and possibly lead to the development of new compositions capable of nanoparticle exsolution with higher activity and stability.

Controllable synthesis of graphene derivatives with defined composition and properties represents the holy grail of graphene chemistry, especially in view of the low reactivity of graphene. Recent progress in fluorographene (FG) chemistry has opened up new routes for synthesizing a plethora of graphene derivatives with widely applicable properties, but they are often difficult to control. We explored nucleophilic substitution on FG combining density functional theory calculations with experiments to achieve accurate control over the functionalization process. In-depth analysis revealed the complexity of the reaction and identified basic rules for controlling the 2D chemistry. Their application, that is, choice of solvent and reaction time, enabled facile control over the reaction of FG with N-octylamine to form graphene derivatives with tailored content of the alkylamine functional group (2.5–7.5% N atomic content) and F atoms (31.5–3.5% F atomic content). This work substantially extends prospects for the controlled covalent functionalization of graphene.

Ions inside of fullerene molecules are model systems for the study of the electrostatic interaction across a single layer of carbon. For TbSc₂N@C₈₀ on h-BN/Ni(111), we observe with high-resolution X-ray photoelectron spectroscopy a splitting of the C 1s core level. The data may be explained quantitatively with density functional theory. The correlation of the C 1s eigenvalues and the Coulomb potential of the inside ions at the corresponding carbon sites indicates incomplete screening of the electric field due to the endohedral ions. The screening comprises anisotropic charge transfer to the carbon atoms and their polarization. This behavior is essential for the ordering of endohedral single-molecule magnets and is expected to occur in any single-layer material.

Two-dimensional valleytronic systems can provide information storage and processing advantages that complement or surpass those of conventional charge- and spin-based semiconductor technologies. The major challenge currently is to realize valley polarization for manipulating the valley degree of freedom. Here, we propose that valley polarization can be readily achieved in Janus single-layer MoSSe through magnetic doping, which is highly feasible in experiment. Due to inversion symmetry breaking combined with strong spin–orbit coupling (SOC), the pure single-layer MoSSe harbors an intriguing multivalleyed band structure and strong coupled spin and valley physics. After doping Cr/V, the long-sought valley polarization is successfully achieved with a remarkable energy difference of ∼0.06 eV upon switching on SOC. Furthermore, the valley polarization in Cr/V-doped single-layer MoSSe is tunable via strain engineering. Our work thus provides a promising platform for experimental studies and applications of the valleytronics.

One of the first steps in designing ferromagnetic (FM) molecular materials of p-block radicals is the suppression of covalent radical–radical interactions that stabilize a diamagnetic ground state. In this contribution, we demonstrate that FM coupling between p-block radicals can be achieved by constructing mixed dimers from different radicals with differing symmetries of their singly occupied molecular orbitals. The applicability of this approach is demonstrated by studying magnetic interactions in organic radical dimers built from different derivatives of the well-known phenalenyl radical. The calculated enthalpies of dimerization for different homo- and heterodimers show that the formation of a mixed dimer with FM coupling is favored compared to the formation of homodimers with antiferromagenetic (AFM) coupling. We argue that cocrystallization of radicals with specifically tuned morphologies of their singly occupied molecular orbitals is a feasible and promising approach in designing new organic magnetic materials.

Understanding Lewis pair (LP) interactions at heterogeneous environments is important for controlling surface reactions. We report the formation of interfacial Lewis adducts with tris(pentafluorophenyl)borane as the Lewis acid and 4-mercaptobenzonitrile attached to gold as the Lewis base. We use the nitrile vibrational frequency as a probe of adduct strength, with stronger adducts leading to larger frequencies. The vibrational frequency shifts of the surface adducts were measured via sum frequency generation spectroscopy and compared to the frequency shifts of bulk adducts. Our results show a distinctly smaller frequency shift for the surface adducts compared to the bulk, indicating a weaker Lewis acid–base interaction near the surface. We explore three possible origins of this difference: interfacial frustration, surface electric fields, and electronic energy level alignment. We highlight the relevance of each and note that likely more than one of them affect the observed surface LP interactions.

The formation relationship between colloidal magic-size clusters (MSCs) and conventional quantum dots (QDs) has not been well established. Here, we report our systematic study on their formation pathways, using cadmium sulfide (CdS) as a model system. Two Cd precursors were prepared from CdO with branched 2-methyloctadecanoic acid (C₁₆H₃₃CH(CH₃)–COOH) and linear oleic acid (C₁₆H₃₁CH₂–COOH), reacting with elemental S powder in 1-octadecene (ODE). We show that the presence of MSC-311 (exhibiting a sharp absorption peaking at 311 nm) is regulated by the growth of conventional QDs. We demonstrate that MSC-311 cannot directly convert into conventional QDs but to its immediate precursor (IP-311), which is transparent in optical absorption (>310 nm). We propose that there are two individual pathways for the formation of MSCs and conventional QDs, linked by an intrinsic pathway from MSCs to IPs to fragments to QDs. The present study introduces new avenues to precisely control their formation.

Recent studies show that perovskites (ABX₃-type) comprising mixed A or B cation and/or mixed halide (X) are more stable and efficient materials for photovoltaic applications than their respective pure forms. Herein we report how doping of a small quantity of formamidinium and/or chloride ion influences the single and multiexciton dynamics of CsPbI₃ nanocrystals (NCs). With the help of ultrafast pump–probe spectroscopic measurements, we show that chloride doping can enhance the biexciton lifetime of the system significantly by slowing down the Auger recombination (AR) process. The measured biexciton AR time scale (∼195–205 ps) in some of these NCs is the longest among those reported to date for any similar size perovskites. We further demonstrate that suppression of the AR rate and consequent lengthening of biexciton lifetime allow harvest of these species for their utilization through rapid (18–45 ps) electron transfer to fullerene. The insights obtained from this study are expected to help design more efficient doped perovskites for energy conversion purposes.

The temperature and depth dependence of the shear viscosity (η) of the quasi-liquid layer (QLL) of water on ice-I_h crystals was determined using simulations of the TIP4P/Ice model. The crystals display either the basal {0001} or prismatic {101̅0} facets, and we find that the QLL viscosity depends on the presented facet, the distance from the solid/liquid interface, and the undercooling temperature. Structural order parameters provide two distinct estimates of the QLL widths, which are found to range from 6.0 to 7.8 Å, and depend on the facet and undercooling temperature. Above 260 K, the viscosity of the vapor-adjacent water layer is significantly less viscous than the solid-adjacent layer and is also lower than the viscosity of liquid water.

We investigate the formation of zeolite structures in replica-exchange Monte Carlo simulations of a reactive model of silica polymerization. The simulations incorporate hard spheres to model the effect of excluded volume caused by structure-directing agents (SDAs). We focus on modeling the formation of cage-type zeolite frameworks SOD and LTA. Our model predicts that a relatively wide range of SDA sizes could be used to construct SOD, whereas a narrower range will work for constructing LTA. We also predict that there is potential benefit of including multiple SDAs in each zeolite unit cell, and in the case of LTA with both small and large cavities, there is a strong potential benefit using both small and large SDAs that match the cavities’ sizes. We hypothesize that the volume exclusion reduces the configuration space available to the assembling silica units, making it easier for the system to find ordered structures with quasi-spherical cavities.

Studying the structure–property relations of tailored dipolar phenyl and biphenylphosphonic acids, we report self-assembled monolayers with a significant decrease in the work function (WF) of indium–tin oxide (ITO) electrodes. Whereas the strengths of the dipoles are varied through the different molecular lengths and the introduction of electron-withdrawing fluorine atoms, the surface energy is kept constant through the electron-donating N,N-dimethylamine head groups. The self-assembled monolayer formation and its modification of the electrodes are investigated via infrared reflection absorption spectroscopy, contact angle measurements, and photoelectron spectroscopy. The WF decrease in ITO correlates with increasing molecular dipoles. The lowest ever recorded WF of 3.7 eV is achieved with the fluorinated biphenylphosphonic acid.

The direct and quantitative identification of active sites is crucial for the development of zeolite catalysts and their implementation in industry. Herein we report on the application of one-dimensional ¹¹⁹Sn direct polarization (DP) and rotational echo double-resonance (REDOR) and two-dimensional ¹¹⁹Sn magic-angle tuning (MAT) NMR spectroscopy for the identification of different Sn sites in fully dehydrated Sn-BEA zeolite. It is demonstrated that ¹¹⁹Sn magic-angle spinning (MAS) NMR techniques, modified by Carr–Purcell–Meiboom–Gill (CPMG) echo-train acquisition allow to resolve three groups of NMR signals, which can be attributed to three groups of nonequivalent T-sites based on the existing theoretical predictions: (I) T9, T4, and T3; (II) T2, T1, and T8; and (III) T7, T5, and T6. Results suggest that the sites attributed to group III are the most populated in Sn-BEA samples obtained via the fluoride route. The attribution of NMR lines to different T-sites in the structure of BEA allows for the establishment of structure–reactivity relationship and therefore for further improvement of Sn-BEA catalysts.

It is known that specific oligomers of single-stranded DNA (ssDNA) can show remarkable selectivity when coating different structural species of single-wall carbon nanotubes (SWCNTs). We report that (ATT)₄ ssDNA coatings strongly distinguish between the two optical isomers of (7,5) SWCNTs. This causes resolvable shifts in their fluorescence spectra and differences of 2 orders of magnitude in the room temperature rates of coating displacement, as monitored through changes in nanotube fluorescence wavelength and intensity on exposure to sodium deoxycholate. During coating displacement, the enantiomer with high affinity for the ssDNA oligomer is deduced to form an intermediate hybrid that is not observed for the low affinity enantiomer. These results reveal that enantiomeric differences in SWCNTs complexed with ssDNA are more diverse and dramatic than previously recognized.