OH Modes Research Articles

Unraveling the Vibrational Spectral Signatures of a Dislocated H Atom in Model Proton-Coupled Electron Transfer Dyad Systems.

Phenol-benzimidazole and phenol-pyridine proton-coupled electron transfer (PCET) dyad systems are computationally investigated to resolve the origins of the asymmetrically broadened H-bonded OH stretch transitions that have been previously reported using cryogenic ion vibrational spectroscopy in the ground electronic state. Two-dimensional (2D) potentials describing the strongly shared H atom are predicted to be very shallow along the H atom transfer coordinate, enabling dislocation of the H atom between the donor and acceptor groups upon excitation of the OH vibrational modes. These soft H atom potentials result in strong coupling between the OH modes, which exhibit significant bend-stretch mixing, and a large number of normal mode coordinates. Vibrational spectra are calculated using a Hamiltonian that linearly and quadratically couples the H atom potentials to over two dozen of the most strongly coupled normal modes treated at the harmonic level. The calculated vibrational spectra qualitatively reproduce the asymmetric shape and breadth of the experimentally observed bands in the 2300-3000 cm-1 range. Interestingly, these transitions fall well above the predicted OH stretch fundamentals, which are computed to be surprisingly red-shifted (<2000 cm-1). Time-dependent calculations predict rapid (<100 fs) relaxation of the excited OH modes and instant response from the lower-frequency normal modes, corroborating the strong coupling predicted by the model Hamiltonian. The results highlight a unique broadening mechanism and complicated anharmonic effects present within these biologically relevant PCET model systems.

Temperature Dependence of Non-Condon Effects in Two-Dimensional Vibrational Spectroscopy of Water.

Non-Condon effects in vibrational spectroscopy refers to the dependence of a molecule's vibrational transition dipole and polarizability on the coordinates of the surrounding environment. Earlier studies have shown that such effects can be pronounced for hydrogen-bonded systems like liquid water. Here, we present a theoretical study of two-dimensional vibrational spectroscopy under the non-Condon and Condon approximations at varying temperatures. We have performed calculations of both two-dimensional infrared and two-dimensional vibrational Raman spectra to gain insights into the temperature dependence of non-Condon effects in nonlinear vibrational spectroscopy. The two-dimensional spectra are calculated for the OH vibration of interest in the isotopic dilution limit where the coupling between the oscillators is ignored. Generally, both the infrared and Raman line shapes undergo red shifts with decrease in temperature due to strengthening of hydrogen bonds and decrease in the fraction of OH modes with weaker or no hydrogen bonds. The infrared line shape is further red-shifted under the non-Condon effects at a given temperature, while the Raman line shape does not show any such red shift due to non-Condon effects. The spectral dynamics becomes slower on decrease of temperature due to slower hydrogen bond relaxation and, for a given temperature, the spectral diffusion occurs at a faster rate upon inclusion of non-Condon effects. The time scales of spectral diffusion extracted from different metrics agree well with each other and also with experiments. The changes in the spectrum due to non-Condon effects are found to be more significant at lower temperatures.

OH Stretching and Libration Bands of Solitary Water in Ionic Liquids and Dipolar Solvents Share a Single Dependence on Solvent Polarity.

Ionic liquids are an emerging class of materials which are finding application in a variety of technologically important areas. Because of their hydrophilic character, at least a small concentration of water is often present when ionic liquids are used in practical applications. This study employs infrared spectroscopy in the OH stretching and libration regions together with DFT calculations to better characterize the state of dilute water in ionic liquids. Water mole fractions (xw ∼ 0.1) are chosen such that nearly all water occurs in monomeric form and spectra probe the solvation structure and dynamics of solitary water molecules. New data are reported for a series of 1-ethyl-3-methylimidazolium liquids [Im21][X] with X- = (C2F5)3F3P-, (CF3SO2)2N-, BF4-, B(CN)4-, CF3SO3-, C2H5SO4-, NO3-, SCN-, and CH3CO2-, as well as for the two 1-hexyl-3-methylimidazolium liquids [Im61][Cl] and [Im61][I]. For comparison, spectra are also recorded in a variety of dipolar solvents, and much of the available literature data are summarized, providing a comprehensive perspective on monomeric water in homogeneous solution. Most prior studies of dilute water in ionic liquids interpreted OH stretching spectra only in terms of water being specifically bonded to two anions in A-···H-O-H···A- type solvates. The more detailed analysis presented here indicates the additional presence of asymmetrically solvated water, which in some cases includes both singly solvated (A-···H-O-H) and more subtle forms of asymmetric solvation. The same pattern of solvation also pertains to dipolar solvents capable of accepting hydrogen bonds from water. No clear distinction is found between OH spectra in high-polarity conventional solvents and ionic liquids. In all solvents, OH frequencies are strongly correlated to measures of solvent basicity or hydrogen bond accepting ability. Far-infrared spectra of the water libration band also show common trends in ionic and dipolar solvents. Despite the different character of the libration and OH modes, the frequencies of these vibrations show virtually the same solvent dependence (apart from sign) except in weakly polar or nonpolar solvents.

A Hessian-Free Method to Prevent Zero-Point Energy Leakage in Classical Trajectories.

The problem associated with the zero-point energy (ZPE) leak in classical trajectory calculations is well known. Since ZPE is a manifestation of the quantum uncertainty principle, there are no restrictions on energy during the classical propagation of nuclei. This phenomenon can lead to unphysical results, such as forming products without the ZPE in the internal vibrational degrees of freedom (DOFs). The ZPE leakage also permits reactions below the quantum threshold for the reaction. We have developed a new Hessian-free method, inspired by the Lowe-Andersen thermostat model, to prevent energy dipping below a threshold in the local-pair (LP) vibrational DOFs. The idea is to pump the leaked energy to the corresponding local vibrational mode taken from the other vibrational DOFs. We have applied the new correction protocol on the ab-initio ground-state molecular dynamics simulation of the water dimer (H2O)2, which dissociates due to unphysical ZPE spilling from high-frequency OH modes. The LP-ZPE method has been able to prevent the ZPE spilling of the OH stretching modes by pumping back the leaked energy into the corresponding modes, while this energy is taken from the other modes of the dimer itself, keeping the system as a microcanonical ensemble.

Mesoporous Cu Catalysts for Dimethyl Oxalate Selective Hydrogenation: Impact of the Cu/Al interface on the Textural Properties and Catalytic Behavior

AbstractIn this paper, mesoporous monometallic Cu catalysts reinforced by the Al3+ dopants with different chemical features were successfully synthesized by controlling the preparation process. The N2‐Adsorption/Desorption, XRD, H2‐TPR, SEM, TEM, H2‐TPD and XPS were conducted to explore the structure evolution of the as‐synthesized samples focusing on the interface effect between Cu nano‐particles (NPs) and Al3+ dopants. It is found that the precipitants used for preparing precursors show drastically effect on the Al3+ chemical form and Cu/Al bonding manners of the as‐synthesized CuAl catalysts, further determining the resultant physicochemical properties and catalytic behavior in dimethyl oxalate (DMO) hydrogenation. In gas‐phase DMO hydrogenation, 98.0 % ethylene glycol (EG) and 90.0 % ethanol (EtOH) yield from DMO selective hydrogenation can be achieved over the CuAl catalyst by regulating the reaction temperature. The correlation between the catalytic behavior and physicochemical features shows that the surface Cu+ sites generated in the Cu/(hydr)oxide interface should be essential for DMO selective hydrogenation in presence of the adequate Cu0 sites. Additionally, the Cu−O−Al patterns in the Cu/Al interface intend to promote more electron transferred from the Al3+ dopants to Cu species through the O bridging, facilitating the CuAl(O) stronger Cu/Al interaction than that of the CuAl(C) catalyst in form of Cu−Al−OH mode. Thus, the Cu NPs growth of the CuAl(O) catalyst was effectively retarded, favoring enhanced catalytic stability.

In situ high temperature spectroscopic study of liquid inclusions and hydroxyl groups in high purity natural quartz

High purity natural based quartz is used as raw material for production of crucibles for solar-grade silicon production. The crucible properties are strongly related to presence of water and hydroxyl groups in the raw material. In this work, in situ temperature-dependent diffuse reflectance infrared (DRIFT) and Raman spectroscopy in the spectral range of the OH stretching modes, 3000–4000 cm−1, were used to investigate water inclusions and hydroxyl groups at temperatures up to 800 °C. DRIFT shows that a substantial amount of liquid water was removed at 700 °C whereas new silanol groups characterised by stretching modes at about 3650 cm−1 were formed above 200 °C. A surface OH mode was also identified by multivariante curve resolution (MCR) of Raman maps. These surface OH groups were interpreted as the sign of formation of a hydrated layer at the surface of inclusions. It was not possible to detect water signals in other types of structural defect like cracks. Images were acquired in an in situ cell showing different stages of the rupture of an inclusion with a diameter of ≈8 μm between 400 and 500 °C. The in situ Raman spectrum of the inclusion water showed the typical liquid water bands at room temperature with a maximum moving to higher wavenumbers with increasing temperature. At 400 °C, the single peak at 3645 cm−1 indicated a situation close to the critical point, triggering rupture. The rupture of such large inclusions was thus identified as the dominating channel for the removal of liquid water inclusions. A small inclusion with a diameter ≈4 μm, however, was stable even at 800 °C. These small inclusions contain supercritical water, as evidenced by the sharp Raman peak at 3600 cm−1. Via the peak position, the internal pressure in this stable inclusion was estimated to be 90 MPa. Stability may be facilitated by the formation of a hydrated interfacial layer; the different reactivities of the inclusion fluid at different temperatures leads to different interfacial structures at different temperatures. The presented evidence suggests that inclusions with diameter in the range of few μm are the main source of remaining water and hydroxyl groups in thermally treated high purity quartz sand.

Water in the crystal structure of CaSiO3 perovskite

Abstract While the water storage capacities of the upper 700 km depths of the mantle have been constrained by high-pressure experiments and diamond inclusion studies, the storage capacity of the lower mantle remains controversial. A recent high-pressure experimental study on CaSiO3 perovskite, which is the third most abundant mineral in the lower mantle, reported possible storage of H2O up to a few weight percent. However, the substitution mechanism for H in this phase remains unknown. We have conducted a series of density functional theory calculations under static-lattice conditions and high pressures to elucidate hydration mechanisms at the atomic scale. All of the possible dodecahedral (Ca2+ → 2H+) and octahedral (Si4+ → 4H+) substitution configurations for a tetragonal perovskite lattice have very small energy differences, suggesting the coexistence of multiples of H configurations in CaSiO3 perovskite at mantle pressures and temperatures. The dodecahedral substitutions decrease the bulk modulus, resulting in a smaller unit-cell volume of hydrous CaSiO3 perovskite under pressure, consistent with the experimental observations. Although the octahedral substitutions also decrease the bulk modulus, they increase the unit-cell volume at 1 bar. The H atoms substituted in the dodecahedral sites develop much less hydrogen bonding with O atoms, leading to a large distortion in the neighboring SiO6 octahedra. Such distortion may be responsible for the non-cubic peak splittings observed in experiments on hydrous CaSiO3 perovskite. Our calculated infrared spectra suggest that the observed broad OH modes in CaSiO3 perovskite can result from the existence of multiples of H configurations in the phase. Combined with the recent experimental results, our study suggests that CaSiO3 can be an important mineral phase to consider for the H2O storage in the lower mantle.

Spatial and temporal variability in the hydroxyl (OH) radical: understanding the role of large-scale climate features and their influence on OH through its dynamical and photochemical drivers

Abstract. The hydroxyl radical (OH) is the primary atmospheric oxidant responsible for removing many important trace gases, including methane, from the atmosphere. Although robust relationships between OH drivers and modes of climate variability have been shown, the underlying mechanisms between OH and these climate modes, such as the El Niño–Southern Oscillation (ENSO), have not been thoroughly investigated. Here, we use a chemical transport model to perform a 38 year simulation of atmospheric chemistry, in conjunction with satellite observations, to understand the relationship between tropospheric OH and ENSO, Northern Hemispheric modes of variability, the Indian Ocean Dipole, and monsoons. Empirical orthogonal function (EOF) and regression analyses show that ENSO is the dominant mode of global OH variability in the tropospheric column and upper troposphere, responsible for approximately 30 % of the total variance in boreal winter. Reductions in OH due to El Niño are centered over the tropical Pacific and Australia and can be as high as 10 %–15 % in the tropospheric column. The relationship between ENSO and OH is driven by changes in nitrogen oxides in the upper troposphere and changes in water vapor and O1D in the lower troposphere. While the correlations between monsoons or other modes of variability and OH span smaller spatial scales than for ENSO, regional changes in OH can be significantly larger than those caused by ENSO. Similar relationships occur in multiple models that participated in the Chemistry–Climate Model Initiative (CCMI), suggesting that the dependence of OH interannual variability on these well-known modes of climate variability is robust. Finally, the spatial pattern and r2 values of correlation between ENSO and modeled OH drivers – such as carbon monoxide, water vapor, lightning, and, to a lesser extent, NO2 – closely agree with satellite observations. The ability of satellite products to capture the relationship between OH drivers and ENSO provides an avenue to an indirect OH observation strategy and new constraints on OH variability.

Hydrogen bond dynamics of interfacial water molecules revealed from two-dimensional vibrational sum-frequency generation spectroscopy

Vibrational sum-frequency generation (vSFG) spectroscopy allows the study of the structure and dynamics of interfacial systems. In the present work, we provide a simple recipe, based on a narrowband IR pump and broadband vSFG probe technique, to computationally obtain the two-dimensional vSFG spectrum of water molecules at the air–water interface. Using this technique, to study the time-dependent spectral evolution of hydrogen-bonded and free water molecules, we demonstrate that at the interface, the vibrational spectral dynamics of the free OH bond is faster than that of the bonded OH mode.

Structural Modifications of Single-Crystal Aragonite CaCO3 Beginning at ~15 GPa: In Situ Vibrational Spectroscopy and X-Ray Diffraction Evidence

The structural chemistry of carbonates under mantle conditions facilitates our understanding of carbon recycling pathways in the earth’s interior. It also has impacts on the dynamics of mantle–slab interactions. Aragonite is a common calcium carbonate mineral in pelagic marine sediments. The structural chemistry of single-crystal aragonite during successive compression and the behavior of a structural H+ have been investigated by micro-vibrational spectroscopy and synchrotron X-ray diffraction techniques in diamond anvil cells. We describe a reduction of the b-axial compressibility beginning at ~15 GPa, and the related discontinuities in the first-order derivatives of the vibrational modes. The structural modifications of aragonite are manifested by mutations occurring in the pressure relations of the wavenumbers of the O-C-O bending modes, and of the bandwidth and band intensities of the measured internal and external modes. These anomalies are indicative of changes occurring in the force constant of the C-O bonds, and possibly a second-order phase transition. Besides, the [CaO9] polyhedra begin to deform, possibly with some Ca-O bonds becoming elongated and the others shortening. An increase in the co-ordination number for the Ca2+ sites could be expected under higher pressures. Additionally, the weakening of the OH modes may imply H+-loss from the aragonite lattice above 11.5 GPa.

Intrinsic physicochemical interactions of calcium hydroxide-based medications.

To investigate intrinsic physicochemical properties and interactions of three different calcium hydroxide-based medications via means of different analytical methods. Two-commercial premixed medications: TempCanal(TCmx) and ProCalR(PCmx) and powder-form ProCal(PCpw) with glycerin were used. Vibrational modes were analyzed using Raman spectroscopy. Spectral mapping of samples was carried out using characteristic vibrational modes of calcium hydroxide and barium sulfate. Crystalline and amorphous phases were studied with X-rays powder diffraction analysis. Topographic features were examined by scanning electron microscope examination and quantitative analysis was determined using energy-dispersive X-ray spectroscopy analysis. Strong OH stretch of in Raman spectra were observed at 3,697 and 3,615 cm-1 for TCmx and reference, respectively. However, OH mode was not observed for PCmx and PCpw. Moreover, some peaks in the fingerprint areas of TCmx and PCpw overlapped with each other. The characteristic vibration bands of barium sulfate and calcium hydroxide were observed in all samples, and no new peak was observed in the Raman spectra of samples. Calcium hydroxide-based medications were seen as differed in their chemical composition. No new crystalline or amorphous phase peak was observed. Only calcium hydroxide and barium sulfate were matched in X-rays powder-diffraction analysis. Energy-dispersive X-ray spectroscopy analysis showed that amount of Ba and S elements in the PCpw were lower than TCmx and PCmx whereas, for Ca in the PCpw was higher than TCmx and PCmx. The present study revealed the structural difference among different forms of calcium hydroxide-based medications. The vehicle and substrates of the tested medications altered the physicochemical properties of the compound via electrostatic interactions.

Large H2O solubility in dense silica and its implications for the interiors of water-rich planets

Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter in [Formula: see text]O-rich setting at high pressures and temperatures ([Formula: see text]) places important limitations on our understanding of this planet type. We have conducted experiments for reactions between [Formula: see text] and [Formula: see text]O as archetypal materials for rock and ice, respectively, at high [Formula: see text] We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where the [Formula: see text]-type (Ct) structure appears at lower pressures than in the anhydrous system. Infrared spectroscopy identified strong OH modes from the dense silica samples. Both previous experiments and our density functional theory calculations support up to 0.48 hydrogen atoms per formula unit of ([Formula: see text])[Formula: see text] At pressures above 60 GPa, [Formula: see text]O further changes the structural behavior of silica, stabilizing a niccolite-type structure, which is unquenchable. From unit-cell volume and phase equilibrium considerations, we infer that the niccolite-type phase may contain H with an amount at least comparable with or higher than that of the Ct phase. Our results suggest that the phases containing both hydrogen and lithophile elements could be the dominant materials in the interiors of water-rich planets. Even for fully layered cases, the large mutual solubility could make the boundary between rock and ice layers fuzzy. Therefore, the physical properties of the new phases that we report here would be important for understanding dynamics, geochemical cycle, and dynamo generation in water-rich planets.

Structure and stretching dynamics of water molecules around an amphiphilic amide from FPMD simulations: A case study of N,N-dimethylformamide

N,N-Dimethylformamide (DMF) is a unique tertiary amphiphilic amide, where the presence of a hydrophilic aldehyde group favors hydrogen bond acceptance, but two hydrophobic methyl substituents inhibit interaction with water molecules. As a result, the water molecules encounter two different environments in the vicinity of DMF molecule: around the hydrophobic nitrogen site; and near the hydrophilic carbonyl oxygen. We employ first principles molecular dynamics methods to simulate an aqueous solution of DMF using PBE functional with Grimme's D3 dispersion correction at 330 K. Investigations on the liquid structure to understand inter-atomic interactions in amides attract much attention. We calculated various structural and dynamical properties along with vibrational stretching frequency of water molecules to understand heterogeneously affected water molecules by an amphiphilic amide molecule. In solvated DMF, the first peak minimum of the N-OW and OC-OW radial distribution functions (‘w’ subscript denotes atoms of water) are located at 5.72 and 3.16 Å, respectively. These distance cutoffs decide the boundary of the solvation shell. At OC-HW distance 2.45 Å, the deep peak minimum indicates stable OC … HW hydrogen bond. Previous Monte Carlo simulations reported the presence of hydrogen bonds between the oxygen site of DMF and hydrogen of water. The time-series wavelet method was used to compute the time-dependent frequencies of the hydroxyl groups of water. The average frequency of the OH modes inside the CO solvation shell (~3364 cm−1) in DMF is higher than bulk (~3337 cm−1), and the trend matches with an aqueous solution of acetone. In nitrogen hydration shell, the intense band resembles the bulk frequency distribution, and a narrow distinctive peak at the high-frequency side (range ~3650–3750 cm−1) represents the non‑hydrogen bonded or dangling OH groups. Raman spectroscopy in hydrophobic TBA and air/water interface displayed dangling OH stretch peak at ~3660 cm−1 and ~3710 cm−1, respectively. Our calculation of the frequency distribution, frequency-frequency correlation function, and hydrogen bond dynamics show the water molecules at bulk behave as in pure water. Inside the solvation shell of aminic nitrogen, non‑hydrogen bonded OH modes with a dangling lifetime ~0.38 ps dominates over the water-water hydrogen bonds. The time-dependent decay of the frequency correlation inside CO solvation shell has three decay components, a rapid decay, then, an intermediate component (~1.52 ps) corresponding to the lifetime of the carbonyl-water hydrogen bond, and the longer timescale ~11.97 ps representing the residence time of water molecules in the vicinity of carbonyl oxygen. We find that the carbonyl-water hydrogen bond (OC … HW) is stronger than the water-water hydrogen bond. The methyl substituents on the nitrogen of DMF impose weak hydrophobic interaction, and the hydrophilic carbonyl oxygen forms a strong hydrogen bond with the neighboring water resulting in localized dynamics.

An in vitro Raman study on compositional correlations of lipids and protein with animal tissue hydration

Raman spectroscopy is a powerful non-invasive tool for detection and classification of chemical composition of materials including biological tissues. In this work, we report an in vitro Raman study on animal skin samples with a focus on high-frequency vibrations such as symmetric CH3 stretching mode at 2934 cm−1, and the symmetric CH2 vibration mode at 2854 cm−1, OH stretching modes near 3412 cm−1, and bounded OH mode near 3284 cm−1. Raman data was acquired with a customized InGaAs based Raman spectrometer that consolidates the NIR (866 nm) light and the InGaAs detector and is particularly suitable for probing high-frequency vibrations. The Raman spectra of fat, tendon, and muscle tissues are also analyzed to determine the spectroscopic identities of CH and OH groups in skin. Our results suggest that the protein is beneficial for the maintenance of skin hydration, as it has higher water capacity and greater capability to retain water than lipids. This conclusion is consistent with the additional discovery that water exists in fat mainly as unbound type, while part of water exists as bound type in muscle.

Aqueous hydroxyl group as the vibrational probe to access the hydrophobicity of amide derivatives

First principles molecular dynamics (FPMD) simulations of relatively dilute aqueous solutions of N-methylformamide (NMF), N, N-dimethylacetamide (DMA), N-methylacetamide (NMA) were carried out to elucidate the effects of variation of hydrophobicity of amide molecules on structure, dynamics and spectral properties of solvating water molecules. A quantitative analysis of dangling OH groups of water molecules, one of the consequences of hydrophobicity, around the amide molecules was performed to explore the structure of surrounding water molecules. We observe that DMA has the most hydrophobic character among the three amide molecules; the lifetime of dangling OH mode of water molecules and the number of such modes are found to be more inside the solvation shell of DMA as compared to NMA and NMF molecules. Overall this lifetime is more inside the solvation shell of amides compared to the bulk water molecules for all aqueous solutions of amides. Rotational dynamics calculation suggests significant retardation of OH bonds of water near the amide oxygen atom (O) due to the OwHw⋯O strong hydrogen bonds. A moderate slowdown of reorientational dynamics is also observed for OH modes that are close to the hydrophobic surface of DMA in its aqueous solution. Vibrational density of states (VDOS) and frequency distribution calculations point out the higher average stretching frequency (~3600–3850 cm−1) of free OH groups. Hydrogen bond lifetime calculations conceive that DMA, having three methyl groups, makes stronger hydrogen bonds through the CO moiety. Vibrational spectral diffusion of bulk water and solvation shell water molecules were also calculated in combination with wavelet transform and frequency-frequency autocorrelation functions. The CO group affected OH stretching frequency bands for aqueous solutions of NMF and NMA molecules are more pronounced than that of DMA. However, NH affected OH frequency bands are less pronounced for NMA and DMA due to the presence of more number of hydrophobic methyl groups. Going from NMF to DMA, the OH frequency bands inside the amide solvation shells shift towards the higher value due to the enhancement of hydrophobicity. The vibrational spectral diffusion of OH modes around CO and NH (N for DMA) groups, as well as for bulk water molecules, is also investigated. Three time scales were found for these calculations for all the cases. The fast time scales in the range ~50–100 fs are due to the amide-water intact hydrogen bonding, and two slower time scales in the range ~0.6–3.90 ps and ~10–20 ps were found. The time scales in the range of ~0.6 to 3.90 ps can be attributed to carbonyl-water and N-H-water hydrogen bonding, and the very long time scales are due to the escape dynamics water molecules from the solvation shell of CO and NH (N for DMA) groups.

Longitudinal electric fields in the OH and ECRH heating modes of the L-2M stellarator

The soft X-ray spectra were measured at the L-2M stellarator in the OH and ECRH modes, which occurred to be considerably non-Maxwellian. In the OH mode, the SXR spectra considerably deviate not only from the Maxwellian spectrum, but also from the model bremsstrahlung spectrum of plasma in the longitudinal electric field. This can be due to the fact that, under ohmic heating conditions, plasma waves can be excited and absorbed by plasma electrons. In the OH mode, the radial distribution of the longitudinal electric field was determined, which turned to be almost uniform over the radius. It was hypothesized that, in the ECRH experiments, the deviations of the measured SXR spectra from the Maxwellian spectrum are also caused by the presence of the longitudinal electric fields in plasma. These fields are the longitudinal vortex electric fields generated in plasma during the current drive.

Time-dependent vibrational sum-frequency generation spectroscopy of the air-water interface

Vibrational sum-frequency generation spectroscopy is a powerful method to study the microscopic structure and dynamics of interfacial systems. Here we demonstrate a simple computational approach to calculate the time-dependent, frequency-resolved vibrational sum-frequency generation spectrum (TD-vSFG) of the air-water interface. Using this approach, we show that at the air-water interface, the transition of water molecules with bonded OH modes to free OH modes occurs at a time scale of sim3 ps, whereas water molecules with free OH modes rapidly make a transition to a hydrogen-bonded state within sim2 ps. Furthermore, we also elucidate the origin of the observed differential dynamics based on the time-dependent evolution of water molecules in the different local solvent environments.

Temperature Dependence of Intramolecular Vibrational Bands in Small Water Clusters.

Cyclic water clusters are pivotal for understanding atmospheric reactions as well as liquid water, yet the temperature (T) dependence of their dynamics and spectroscopy is poorly studied. The development of highly accurate water potentials, such as MB-pol, partly rectifies this. It remains to account for the quantum nuclear effects (NQE), because quantum nuclear dynamics become increasingly inaccurate at low temperatures. From a practical point of view, we find that NQE can be accounted for simply by subtracting a constant from the frequencies obtained from the velocity autocorrelation functions (VACF) of classical nuclear dynamics, resulting in unprecedented agreement with experiment, mostly within 5 cm-1. We have performed classical simulations of (H2O)n clusters (n = 2-5) from 20 K and up to their melting temperature, calculating both all-atom and partial VACF, thus generating the temperature dependence of the vibrational frequencies (IR and Raman bands). Focusing on the hydrogen-bonded (HBed) OH stretch and HOH bend, we find opposing T dependencies. The HBed OH modes blue shift linearly with T, attributed to ring expansion rather than any specific conformational change. The lowest-frequency Raman concerted mode is predicted to show the largest such shift. In contrast, the HOH bend undergoes a red-shift, with the highest frequency concerted band undergoing the largest red-shift. These results can be explained by a coupled-oscillator model for n hydrogen atoms on a ring, constrained to move either tangentially (stretch) or perpendicularly (bend) to the ring. With increasing temperature and weakening of HBs, the intrinsic force constant increases (stretch) or remains constant (bend), while the nearest-neighbor coupling constant decreases, and this results in the interesting behavior revealed herein. T-dependent Raman studies are required for testing some of these predictions.

Dynamics and Spectral Response of Water Molecules around Tetramethylammonium Cation.

Till now, there has been ambiguity about the structural heterogeneity inside a solute solvation shell and the dynamical response of the surrounding solvent molecules. To address the dynamics and spectral response of solvent molecules, we performed first-principles molecular dynamics simulations for the comprehensive study of water's hydroxyl stretch frequency evolution due to environmental variations (also called "spectral diffusion") in the vicinity of a hydrophobe, tetramethylammonium (TMA) cation. The N-Ow radial distribution function (RDF), spatial distribution function (SDF), and combined distribution function (CDF) were calculated to provide information about the arrangement of water molecules around TMA. In the probability distribution plot of the cosine of the angle (θ) between Ow-Hw and NTMA-Ow bond vectors, the hydrogen atoms are observed being oriented toward TMA and the oxygen atoms aligned away. The decaying dynamics of the orientation autocorrelation function (OACF) reveals the reorientation time is more inside the solvation shell (4.1 ps) as compared to bulk (2.8 ps), matching with the trend obtained from water's orientational dynamics in tetraalkylammonium salts. Wavelet transform of the obtained trajectory was used to calculate the time-dependent vibrational stretching frequencies of the OH modes of water molecules. The normalized frequency distribution in the aqueous solvation shell of TMA, tagging a particular water molecule within the N-Ow cutoff distance 5.5 Å, displays an intense peak at 3661 cm-1 representing non-hydrogen bonded or dangling or free OH modes. Simulations around aromatic solutes and Raman-MCR studies in the hydration shell of hydrophobic TBA reported a distinctive dangling OH band at 3660 cm-1 (range: 3661 ± 2 cm-1). Besides dangling water molecules in the first hydration layer of ammonium nitrogen, few OH modes are strongly hydrogen-bonded having an average frequency at 3300 cm-1. The predominance of dangling hydroxyl modes around apolar hydrophobic TMA was further explored by comparing the dangling lifetime (∼0.68 ps) with the lifespan of hydrogen bonded OH modes (∼0.48 ps). At our simulation temperature 330 K, a significant fraction of the water molecules in the vicinity of TMA ion are free or dangling, and a few of them form an ordered structure with enhanced hydrogen bonding. Structural analysis, orientation correlation, frequency fluctuations, dangling, and hole dynamics calculations provide the evidence of the existence of dangling OH modes dominating over highly ordered strong hydrogen bonded structure in the cationic TMA solvation shell at an elevated temperature.

Investigate interactions of water with mesoporous ceria using in situ VT-DRIFTS

The interactions of water with synthesized mesoporous ceria nanoparticles are studied as a function of temperature at two water vapor partial pressures, using in situ Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS). The Variable Temperature (VT)-DRIFTS spectra of mesoporous ceria nanoparticles exhibit six hydroxyl (OH) stretching bands, suggesting both molecular and dissociation of water coexist on mesoporous ceria surfaces and involve hydrogen-bonds. The vibration frequency of individual OH mode is repeatable and the adsorption of water is reversible on various sites between four annealing and water exposure cycles lasting for 60 h, suggesting that the same types of active sites are available on mesoporous ceria surface for water adsorption, with less than 10% of reduction in the numbers of adsorption sites. The results, from this study of reactivity of water on ordered mesoporous ceria nanoparticles under operando conditions, assist in processes benefiting from the hydroxylated surface for improved reaction outcomes, and rational design of mesoporous materials for their application in photocatalysis and heterogeneous catalysis.