We present a first-principles theoretical study of vibrational spectral diffusion and hydrogen bond dynamics in heavy water without using any empirical model potentials. The calculations are based on ab initio molecular dynamics simulations for trajectory generation and a time series analysis using the wavelet method for frequency calculations. It is found that, in deuterated water, although a one-to-one relation does not exist between the instantaneous frequency of an OD bond and the distance of its associated hydrogen bond, such a relation does hold on average. The dynamics of spectral diffusion is investigated by means of frequency-time correlation and spectral hole dynamics calculations. Both of these functions are found to have a short-time decay with a time scale of approximately 100 fs corresponding to dynamics of intact hydrogen bonds and a slower long-time decay with a time constant of approximately 2 ps corresponding to lifetimes of hydrogen bonds. The connection of the slower time scale to the dynamics of local structural relaxation is also discussed. The dynamics of hydrogen bond making is shown to have a rather fast time scale of approximately 100 fs; hence, it can also contribute to the short-time dynamics of spectral diffusion. A damped oscillation is also found at around 150-200 fs, which is shown to have come from underdamped intermolecular vibrations of a hydrogen-bonded water pair. Such assignments are confirmed by independent calculations of power spectra of intermolecular motion and hydrogen bond kinetics using the population correlation function formalism. The details of the time constants of frequency correlations and spectral shifts are found to depend on the frequencies of chosen OD bonds and are analyzed in terms of the dynamics of hydrogen bonds of varying strengths and also of free non-hydrogen-bonded OD groups.

A theoretical study of vibrational spectral diffusion and hydrogen bond dynamics in aqueous ionic solutions is presented from first principles without employing any empirical potential models. The present calculations are based on ab initio molecular dynamics for trajectory generation and wavelet analysis of the simulated trajectories for time dependent frequency calculations. Results are obtained for two different deuterated aqueous solutions: the first one is a relatively dilute solution of a single Cl(-) ion and the second one is a concentrated solution of NaCl ( approximately 3M) dissolved in liquid D(2)O. It is found that the frequencies of OD bonds in the anion hydration shell, i.e., those which are hydrogen bonded to the chloride ion, have a higher stretch frequency than those in the bulk water. Also, on average, the frequencies of hydration shell OD modes are found to increase with increase in the anion-water hydrogen bond distance. On the dynamical side, when the vibrational spectral diffusion is calculated exclusively for the hydration shell water molecules in the first solution, the dynamics reveals three time scales: a short-time relaxation ( approximately 200 fs) corresponding to the dynamics of intact ion-water hydrogen bonds, a slower relaxation ( approximately 3 ps) corresponding to the lifetimes of chloride ion-water hydrogen bonds, and another longer-time constant ( approximately 20 ps) corresponding to the escape dynamics of water from the anion hydration shell. Existence of such three time scales for hydration shell water molecules was also reported earlier for water containing a single iodide ion using classical molecular dynamics [B. Nigro et al., J. Phys. Chem. A 110, 11237 (2006)]. Hence, the present study confirms the basic results of this earlier work using a different methodology. However, when the vibrational spectral diffusion is calculated over all the OD modes, only two time scales of approximately 150 fs and approximately 2.7 ps are found without the slowest component of approximately 20 ps. This is likely because of the very small weight that the hydration shell water molecules carry to the overall spectral diffusion in the solution containing a single ion. For the concentrated solution also, the slowest component of approximately 20 ps is not found in the spectral diffusion of all water molecules because a distinct separation between the hydration shell and bulk water in terms of their stretch frequencies does not hold at this high concentration regime. The present first principles results are compared with those of the available experiments and classical simulations.

Clusters of methanol and ethanol formed above neat liquid samples were entrained in a supersonic jet of helium and probed in the expansion using 118 nm vacuum ultraviolet laser single-photon ionization/time-of-flight (TOF) mass spectrometry. Almost every cluster ion observed in the TOF mass spectra could be represented by the formula H(ROH)n+, where R=CH3 or C2H5, and n=1–5. Formation of these species is attributed to a well-established ionization pathway where each protonated (n−1)-mer originates from its n-mer neutral parent. Signals in the TOF mass spectra due to the protonated trimers H(CH3OH)3+ and H(CH3CH2OH)3+ were found to be the most intense and provides direct evidence that these particular cluster ions are “magic-number” structures. The possible relationships between the observed ion data and the neutral cluster vapor phase distributions are discussed. In this context, methanol and ethanol vapor cluster distributions at 298.15 K and at several pressures⩾the equilibrium vapor pressure were computed using the grand canonical Monte Carlo and molecular dynamics techniques. Lastly, differences between these experiments and the results of bimolecular reaction studies are discussed.

We have carried out a series of molecular dynamics simulations to investigate the hydrogen bond and residence dynamics of X(-)-water (X=F, Cl, and I) and pairs in aqueous solutions at a temperature of 673 K. The calculations are done at six different water densities ranging from 1.0 to 0.15 g cm(-3). The hydrogen bonds are defined by using a set of configurational criteria with respect to the anion(oxygen)-oxygen and anion(oxygen)-hydrogen distances and the anion(oxygen)-oxygen-hydrogen angle for an anion(water)-water pair. The F(-)-water hydrogen bonds are found to have a longer lifetime than all other hydrogen bonds considered in the present study. The lifetime of Cl(-)-water hydrogen bonds is shorter than that of F(-)-water hydrogen bonds but longer than the lifetime of water-water hydrogen bonds. The lifetimes of I(-)-water and water-water hydrogen bonds are found to be very similar. Generally, the lifetimes of both anion-water and water-water hydrogen bonds are found to be significantly shorter than those found under ambient conditions. In addition to hydrogen bond lifetimes, we have also calculated the residence times and the orientational relaxation times of water molecules in ion(water) hydration shells and have discussed the correlations of these dynamical quantities with the observed dynamics of anion(water)-water hydrogen bonds as functions of the ion size and density of the supercritical solutions.

This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

First principle molecular dynamics (FPMD) simulations in the isobaric-isothermal ensemble were carried out to investigate the liquid phase of pure tetramethyl ammonium fluoride (TMAF), its equimolar mixture with water, and its dilute solution in water. These simulations were performed using Born-Oppenheimer molecular dynamics with the quantum many-body potentials and forces obtained directly from on-the-fly electronic structure calculations at the Kohn-Sham density functional theory level. For the equimolar mixture, simulations were carried out using two different generalized gradient approximation functionals and two values of the charge density cutoff, and it is found that thermodynamic properties are rather sensitive to these details of the electronic structure calculations. The FPMD simulation for neat TMAF at a temperature of 600 K did not yield any indication for the decomposition of TMAF over the 50 ps production period, but trimethylamine and fluoromethane decomposition products were found during a short trajectory at 1200 K. At 400 K and 1 atm, the simulations indicate that significant structural rearrangement and changes in cohesive energy density and compressibility occur upon addition of water to TMAF. The hydration water is found to preferentially solvate the fluoride ions, and the distribution of F(-)-H(2)O hydrogen bond lifetimes is broad. The simulations do not reveal any significant differences in the transport behavior of TMA(+), F(-), and H(2)O over the production periods.

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.

We performed Car-Parrinello molecular dynamics (CPMD) simulations of deuterated aqueous solution of methylamine (MA) to investigate the structure, dynamics and time dependent vibrational spectra of water molecules in the first solvation shell. Our results show that the hydrogen bond of DOD…ND 2 is the dominant interaction between ND 2 and D 2 O as compared to the D 2 O…D 2 N. The hydrogen bond involving DOD…ND 2 has longer lifetime (2.6 ps) than both D 2 O…D 2 N (1.1 ps) and waterwater hydrogen bonds. The residence time of water molecule inside the first solvation shell of ND 2 is 5.72 ps. The vibrational spectral diffusion of water molecules in the first hydration shell of the amine nitrogen of methylamine proceeds with three time scales. A short-time relaxation originates from dynamics of amine-water hydrogen bonds without breaking (90 fs), and a slower relaxation (~1.8 ps) is due to the breaking of aminewater hydrogen bonds. Another longer time constant (~7 ps) is due to the escape dynamics of water molecules from the first hydration shell of the amine group.[a] S. Biswas