Frequency Time Correlation Function Research Articles

Nuclear quantum effects on the vibrational dynamics of the water-air interface.

We have applied path-integral molecular dynamics simulations to investigate the impact of nuclear quantum effects on the vibrational dynamics of water molecules at the water-air interface. The instantaneous fluctuations in the frequencies of the O-H stretch modes are calculated using the wavelet method of time series analysis, while the time scales of vibrational spectral diffusion are determined from frequency-time correlation functions and joint probability distributions. We find that the inclusion of nuclear quantum effects leads not only to a redshift in the vibrational frequency distribution by about 120 cm-1 for both the bulk and interfacial water molecules but also to an acceleration of the vibrational dynamics at the water-air interface by as much as 35%. In addition, a blueshift of about 45 cm-1 is seen in the vibrational frequency distribution of interfacial water molecules compared to that of the bulk. Furthermore, the dynamics of water molecules beyond the topmost molecular layer was found to be rather similar to that of bulk water.

Theoretical Two Dimensional Infrared Spectroscopy of Aqueous Solutions of tert-Butyl Alcohol: Variation of the Dynamics of Spectral Diffusion along the Percolation Transition.

Binary mixtures of water and tert-butyl alcohol (TBA) are known to exhibit the so-called percolation transition where small clusters of TBA molecules span into large aggregates beyond a threshold concentration of the alcohol. In the present study, we have investigated the linear and two-dimensional infrared spectral features of aqueous solutions of TBA for varying concentration of the alcohol along the percolation transition. The percolation transition is characterized through calculations of intermolecular radial distribution functions and average size of the largest cluster of TBA molecules. It is found that, with variation of alcohol concentration, the radial distribution functions of the central carbon atoms of TBA molecules show a nonmonotonic change in the height of the first peak and also the size of the largest cluster of TBA molecules show a jump in the increase of its size for TBA mole fraction between 0.04 and 0.06 corresponding to a transition from smaller clusters to larger spanning aggregates. However, it is found that the linear infrared spectrum of water does not exhibit any noticeable changes on variation of TBA concentration along the percolation transition. Subsequently, two-dimensional infrared (2DIR) spectra and vibrational frequency time correlation function of water are calculated for all the TBA-water solutions considered in this study. The spectral diffusion of water calculated from 2DIR is found to slow down with increase of the TBA concentration. The time scales of spectral diffusion of water, as characterized by the relaxation of frequency time correlation function, 2DIR metric of central line slope, and also the hydrogen bond time correlation functions, are found to exhibit a noticeable jump along the percolation transition. The hydrophilic group of TBA is found to retard the water dynamics more effectively than the hydrophobic groups. Also, the jump in the dynamical slowdown along the percolation transition is found to be more significant for water molecules at the hydrophilic sites.

Ionic Dynamics and Vibrational Spectral Diffusion of a Protic Alkylammonium Ionic Salt through Intrinsic Cationic N-H Vibrational Probe from FPMD Simulations.

We employed density functional theory (DFT)-based molecular dynamics simulations to explore the structure, dynamics, and spectral properties of the protic ionic entity trimethylammonium chloride (TMACl). Structural investigations include calculating the site-site radial distribution functions (RDFs), the distribution of constituent cations and anions in three-dimensional space, and combined distribution functions of the hydrogen-bonded pair RDF versus angle, revealing the structural characteristics of the ionic solvation and the intermolecular interactions within ions. Further, we determined the instantaneous vibrational stretching frequencies of the intrinsic N-H stretch probe modes by applying the time-series wavelet method. The associated ionic dynamics within the protic ionic compound were investigated by calculating the time-evolution of the fluctuating frequencies and the frequency-time correlation functions (FFCFs). The time scale related to the local structural relaxation process and the average hydrogen bond lifetime, ion cage dynamics, and mean squared displacement were investigated. The faster decay component of the FFCFs, depicting the intermolecular motion of intact hydrogen bonds in TMACl, is 0.07 ps for the Perdew-Burke-Ernzerhof (PBE)-based simulation and 0.06 ps for the PBE-D2 representation. The slower time scale of the longer picosecond decay time component of PBE and PBE-D2 representations are 3.13 and 2.87 ps, respectively. These picosecond time scales represent more significant fluctuations of the hydrogen-bonding partners in the ionic entity and hydrogen-bond jump events accompanied by large angular jumps. The longest picosecond time scales represent structural relaxation, including large angular jumps and ion-pair dynamics. Also, ion cage lifetimes correlate with the slowest time scale of the associated dynamics of vibrational spectral diffusion despite the type of DFT functional. This study benchmarks DFT treatments of the exchange-correlation functional with and without the van der Waals (vdW) dispersion correction scheme. The inclusion of vdW interactions to the PBE functional represents a less structured state of the ionic entity and faster dynamics of the molecular motions relative to the one predicted by the PBE system. All the results illustrate the necessity of accurately describing the Coulomb interactions, vdW dispersive interactive forces, and localized hydrogen bonds required to sustain the energetic balance in this ionic salt.

On the role of hydrogen-bond exchanges in the spectral diffusion of water

The dynamics of a vibrational frequency in a condensed phase environment, i.e., the spectral diffusion, has attracted considerable interest over the last two decades. A significant impetus has been the development of two-dimensional infrared (2D-IR) photon-echo spectroscopy that represents a direct experimental probe of spectral diffusion, as measured by the frequency-frequency time correlation function (FFCF). In isotopically dilute water, which is perhaps the most thoroughly studied system, the standard interpretation of the longest timescale observed in the FFCF is that it is associated with hydrogen-bond exchange dynamics. Here, we investigate this connection by detailed analysis of both the spectral diffusion timescales and their associated activation energies. The latter are obtained from the recently developed fluctuation theory for the dynamics approach. The results show that the longest timescale of spectral diffusion obtained by the typical analysis used cannot be directly associated with hydrogen-bond exchanges. The hydrogen-bond exchange time does appear in the decay of the water FFCF, but only as an additional, small-amplitude (<3%) timescale. The dominant contribution to the long-time spectral diffusion dynamics is considerably shorter than the hydrogen-bond exchange time and exhibits a significantly smaller activation energy. It thus arises from hydrogen-bond rearrangements, which occur in between successful hydrogen-bond partner exchanges, and particularly from hydrogen bonds that transiently break before returning to the same acceptor.

Vibrational echo spectroscopy of aqueous sodium bromide solutions from first principles simulations.

A theoretical study of the time-dependent vibrational echo spectroscopy of sodium bromide solutions in deuterated water at two different concentrations of 0.5 and 5.0 M and at temperatures of 300 and 350 K is presented using the method of ab initio molecular dynamics simulations. The instantaneous fluctuations in frequencies of local OD stretch modes are calculated using time-series analysis of the simulated trajectories. The third-order polarization and intensities of three pulse photon-echo are calculated from ab initio simulations. The timescales of vibrational spectral diffusion are determined from the frequency time correlation functions (FTCF) and short-time slope of three pulse photon echo (S3PE) calculated within the second-order cumulant and Condon approximations. It is found that under ambient conditions, the rate of vibrational spectral diffusion becomes slower with increase in ionic concentration. Decay of S3PE calculated for different systems give timescales, which are in close agreement with those of FTCF and also with the results of experimental time-dependent vibrational spectroscopic experiments. © 2019 Wiley Periodicals, Inc.

Heterogeneous Occupancy and Vibrational Dynamics of Spatially Patterned Water Molecules.

We performed first-principles molecular dynamics simulations of relatively dilute aqueous solutions of sulfate and thiosulfate dianions to analyze the structure, dynamics, and vibrational spectral properties of water molecules around the solute, especially the spatially patterned solvent molecules in the first solvation layer and the extended layers. This study also involves the investigation of dynamics of dangling OH groups in these layers and their role in patterning the water molecules around the dianions. Structural evaluation of the systems is carried out by radial distribution functions, number integrals, and spatial distribution functions. The lifetime of dangling OH groups inside the solvation shell is compared more to that of the bulk. By constructing the O-H groups in three ensembles (S1, S2, and S3) around the anion, we show that the frequency distribution of OH modes in the S1 ensemble show red-shifting for both sulfate and thiosulfate. The O-H groups in the S2 ensemble of the sulfate-water system show red-shifting by 10 cm-1, while in the case of thiosulfate-water, these O-H groups show blue-shifting by 8 cm-1. The water molecules in S1 and S2 subensembles have slower dynamics compared to those in the bulk (S3). The dynamics of various kinds of hydrogen bonds were characterized by hydrogen bond population correlation functions. The spectral diffusion of solvation shell O-H modes was performed through a frequency-time correlation function. We find a significant amount of orientational retardation of water molecules in the S1 layer and moderate retardation in the S2 layer as compared to that in the bulk, S3 layer. All these findings, the red shift of the OH stretching frequency in S1 and S2 layers, slowing down of the orientational dynamics of OH vectors in S1 and S2 layers, and less diffusivity of water in S1 and S2 layers, show the long-range kosmotropic effect of multivalent sulfate and thiosulfate oxyanions. Due to the long-range effect, heterogeneous occupancy of water molecules is observed, and the water molecules are found to arrange in a patterned manner in the vicinity of anions with varied local density.

Urea in Water: Structure, Dynamics, and Vibrational Echo Spectroscopy from First-Principles Simulations.

Aqueous solution of urea at a concentration of 4.0 M is studied by using ab initio molecular dynamics simulation. The radial and spatial distribution functions reveal no significant disruption of the local solvent structure by urea even at such a rather high concentration. Although the static structural features are not altered in any significant manner, the translational, rotational, and vibrational dynamics are found to show noticeable slowing down. The diffusion coefficient of urea is found to be three times lower than that of bulk water molecules. Similarly, orientational relaxation of water molecules in the solvation shell of urea is found to be about 5.0 ps which is significantly higher than the average value of 3.8 ps found for all water molecules. The vibrational dynamics is investigated through calculations of frequency-time correlation function (FTCF), joint frequency probability, and frequency-structure correlation functions. The timescale of vibrational spectral diffusion as determined from FTCF is found to be 2.7 ps which is higher than the known calculated timescale of ∼2 ps for spectral diffusion of pure water for similar levels of calculations. The third-order polarization and the corresponding vibrational echo intensity of OD modes are calculated within the Condon and second-order cumulant approximations. The timescales of loss of correlation in the vibrational echo spectrum are calculated from the time dependence of the slope of the 3-pulse photon echo (S3PE) function. The timescales obtained from S3PE are found to be in agreement with the FTCF. The slowing down of vibrational, translational, and rotational dynamics means that urea affects the properties of water from a dynamical perspective.

Temperature dependence of the ultrafast vibrational echo spectroscopy of OD modes in liquid water from first principles simulations.

The rate of vibrational spectral diffusion of OD/OH stretch modes of water is known to be interconnected with the hydrogen bond rearrangement dynamics in aqueous media as found in several recent experiments and molecular simulations. In the present study, the temperature dependence of vibrational spectral diffusion of OD stretch modes in liquid water is investigated from first principles by using the method of ab initio molecular dynamics. Kinetic rates obtained from the frequency time correlation function (FTCF), the slope of the 3-pulse photon echo (S3PE) and local structure correlation functions are used in the Arrhenius equation to determine the energy barrier for hydrogen bond rearrangement in liquid water. The slope of the 3-pulse photon echo is determined within the cumulant and Condon approximations. Although the trend found at the low temperature is slightly non-Arrhenius, the barrier for hydrogen bond rearrangement is found to be around 4.2 kcal mol-1 from all the metrics considered here. It is in good agreement with the hydrogen bond energy determined from different experiments and theoretical studies. Based on the findings, a strong correlation between the vibrational spectral diffusion timescale and hydrogen bond dynamics is identified, which gets even more pronounced at low temperatures. Spatio-temporal correlations between frequency fluctuations and the local hydrogen bond network are also explored.

On the Hydrogen Bond Strength and Vibrational Spectroscopy of Liquid Water

In the present work, we introduce two new metrics i.e. hydrogen-bond strength and charge-transfer between the donor/acceptor water molecules as a measure of hydrogen-bond rearrangement dynamics. Further, we also employ a simple model based on energy flux through the donor-acceptor water pairs to quantify the extent of the local hydrogen-bond network reorganization. Most importantly, we report a linear relationship between the OH stretch frequency and the charge and energy transfer through donor-acceptor water pairs. We demonstrate that the vibrational frequency fluctuations, which are used to determine third-order non-linear spectroscopic observables like the short-time slope of three pulse photon echo, can be used as an analog of the fluctuations in the hydrogen-bond strength and charge-transfer. The timescales obtained from our hydrogen-bond strength correlation and charge-transfer correlation decay are in excellent agreement with the computed frequency-time correlation function, as well as with recent vibrational echo experiments.

Vibrational spectral diffusion in supercritical deuterated ammonia from first principles simulations: Roles of hydrogen bonds, free ND modes and inertial rotation of ammonia molecules

We have presented a first principles study of the vibrational spectral diffusion and related dynamical and structural properties of supercritical ammonia at two different densities by means of ab initio molecular dynamics and time series analysis. The ab initio simulations are performed using two density functionals for the electronic structure calculations: one without any dispersion corrections and the other with dispersion corrections. Apart from calculating the dynamics of frequency fluctuations of ND modes of deuterated ammonia in supercritical states, we have also at many other related quantities such as the dynamics of hydrogen bonds and free ND groups, rotational and translational motion of ammonia molecules and also some of the equilibrium quantities such as local density distributions, pair correlations, hydrogen bonding properties and dipole distribution of ammonia molecules. It is found that the hydrogen bonding between ammonia molecules decreases significantly as we move to the supercritical state of lower density from the normal liquid phase. The inclusion of dispersion interactions is found to increase the structural correlations and also the number of hydrogen bonds to some extent. Our calculations of ND frequency distributions reveal that as we move from normal to the supercritical states, the frequency distributions become narrower and show a shift toward the higher frequencies which is in general agreement with experimental results. the frequency time correlation function of the ND modes of ammonia molecules. The frequency time correlation function of the ND modes of ammonia molecules in the supercritical states is found to decay with two time scales: One around 80–100 fs and the other one falls in the region of 350–700 fs. Our calculations of the dynamics of hydrogen bonds, free ND modes and also rotational motion of ND groups in supercritical ammonia reveal that the fast hydrogen bond breaking and inertial rotational motion of ND bonds contribute to the faster component of spectral diffusion of ND bonds while the slower component originates from the dynamics of non-hydrogen-bonded free ND bonds.

Nuclear quantum effects on the vibrational dynamics of liquid water.

Based on quantum-mechanical path-integral molecular dynamics simulations, the impact of nuclear quantum effects on the vibrational and hydrogen bond dynamics in liquid water is investigated. The instantaneous fluctuations in the frequencies of the O-H stretch modes are calculated using the wavelet method of time-series analysis, while the time scales of the vibrational spectral diffusion are determined from frequency-time correlation functions, joint probability distributions, and the slope of three-pulse photon echo. We find that the inclusion of nuclear quantum effects leads not only to a redshift of the vibrational frequency distribution by around 130 cm-1 but also to an acceleration of the vibrational dynamics by as much as 30%. In addition, quantum fluctuations also entail a significantly faster decay of correlation in the initial diffusive regime, which is in agreement with recent vibrational echo experiments.

Vibrational echo spectral observables and frequency fluctuations of hydration shell water around a fluoride ion from first principles simulations

Aqueous solution of a fluoride ion at 300 K is studied using the method of ab initio molecular dynamics simulation. Instantaneous fluctuations in vibrational frequencies of local OD stretch modes of deuterated water are calculated using a time-series analysis of the simulated trajectory. The vibrational spectral diffusion of OD modes in the first and second solvation shells and also in bulk of the aqueous fluoride ionic solution are studied through calculations of the frequency time correlation function (FTCF), joint probability distributions, slope of three pulse photon echo (S3PE) and two dimensional infrared spectrum (2D-IR). The vibrational spectral dynamics in the first solvation shell shows decay with three components which can be correlated with the dynamics of intact ion-water hydrogen bonds, ion-water hydrogen bond lifetime and the escape dynamics of water molecules from the solvation shell. The vibrational spectral diffusion of OD modes in the second solvation shell and in the bulk show very similar decay behavior. The timescales obtained from FTCF, S3PE and the slope of nodal line (SNL) of 2D-IR are found to be in reasonable agreement with each others. Solvation shell dynamics of water molecules in different solvation shells of fluoride ion is studied using vibrational echo spectral observables from first principles simulations. The decay of FTCF, S3PE and SNL for water molecules in first solvation shell show multiple timescales which can be associated with ion-water hydrogen bond lifetime and residence time of water in the solvation shell.

Ultrafast Vibrational Echo Spectroscopy of Liquid Water from First-Principles Simulations.

Vibrational echo spectroscopy has become a powerful technique to study vibrational spectral diffusion in water and aqueous solutions. The dynamics of vibrational spectral diffusion is intimately related to the hydrogen bond fluctuations in liquid water and other hydrogen bonded liquids. Earlier theoretical calculations of vibrational echo spectroscopy of aqueous systems were based on classical molecular dynamics simulations involving empirical force fields of water. In the current work, we have employed the method of ab initio molecular dynamics simulation to calculate the spectral observables of vibrational echo and two-dimensional infrared (2D-IR) spectroscopy of liquid water at room temperature under Condon and cumulant approximations. The time scales extracted from the temporal decay of the frequency-time correlation function (FTCF), short-time slope of three pulse photon echo (SP3E), dynamic line width (DLW), and the slope of nodal line of 2D-IR spectra are found to be in reasonably close agreement with each other which reinforces the assertion that signatures of FTCF can be captured using three pulse photon echo and 2D-IR spectroscopy.

Ultrafast phosphate hydration dynamics in bulk H2O.

Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H2PO4(-) ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. Two-dimensional infrared spectra of the symmetric (νS(PO2(-))) and asymmetric (νAS(PO2(-))) PO2(-) stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH)2) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the νS(PO2(-)) and νAS(PO2(-)) transition frequencies with larger frequency excursions for νAS(PO2(-)). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO2(-)) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H2PO4(-)/H2O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water.

Molecular Dynamics Investigation of the Vibrational Spectroscopy of Isolated Water in an Ionic Liquid

Experimental studies examining the structure and dynamics of water in ionic liquids (ILs) have revealed local ion rearrangements that occur an order of magnitude faster than complete randomization of the liquid structure. Simulations of an isolated water molecule embedded in 1-butyl-3-methyl imidazolium hexafluorophosphate, [bmim][PF6], were performed to shed insight into the nature of these coupled water-ion dynamics. The theoretical calculations of the spectral diffusion dynamics and the infrared absorption spectra of the OD stretch of isolated HOD in [bmim][PF6] agree well with experiment. The infrared absorption line shape of the OD stretch is narrower and blue-shifted in the IL compared to those in aqueous solution. Decomposition of the OD frequency time correlation function revealed that translational motions of the anions dominate the spectral diffusion dynamics.

Amide-I Characteristics of Helical β-Peptides by Linear Infrared Measurement and Computations

In this work, we have examined the amide-I characteristics of three β-peptide oligomers in typical helical conformations (two in 14-helix and one in 12/10-helix), solvated in water, methanol, and chloroform, respectively. Local-mode frequencies and their distributions were computed using a molecular-mechanics force field based frequency map that was constructed on the basis of molecular dynamics simulations. The local-mode frequencies were found to be determined primarily by peptide backbone and side chain, rather by solvent, suggesting their local structural sensitivities. Intermode vibrational couplings computed using a transition dipole scheme were found to be very sensitive to peptide conformation, with their signs and magnitudes varying periodically along the peptide chain. Linear infrared absorption spectra of the three peptides, simulated using a frequency-frequency time-correlation function method, were found to be in fair agreement with experimental results. Normalized potential energy distribution analysis indicated that the amide-I mode can delocalize over a few amide units. However, the IR band structure appears to be more sophisticated in helical β-peptides than in helical α-peptides.

Dynamics of supercritical methanol of varying density from first principles simulations: Hydrogen bond fluctuations, vibrational spectral diffusion, and orientational relaxation

A first principles study of the dynamics of supercritical methanol is carried out by means of ab initio molecular dynamics simulations. In particular, the fluctuation dynamics of hydroxyl stretch frequencies, hydrogen bonds, dangling hydroxyl groups, and orientation of methanol molecules are investigated for three different densities at 523 K. Apart from the dynamical properties, various equilibrium properties of supercritical methanol such as the local density distributions and structural correlations, hydrogen bonding aspects, frequency-structure correlations, and dipole distributions of methanol molecules are also investigated. In addition to the density dependence of various equilibrium and dynamical properties, their dependencies on dispersion interactions are also studied by carrying out additional simulations using a dispersion corrected density functional for all the systems. It is found that the hydrogen bonding between methanol molecules decreases significantly as we move to the supercritical state from the ambient one. The inclusion of dispersion interactions is found to increase the number of hydrogen bonds to some extent. Calculations of the frequency-structure correlation coefficient reveal that a statistical correlation between the hydroxyl stretch frequency and the nearest hydrogen-oxygen distance continues to exist even at supercritical states of methanol, although it is weakened with increase of temperature and decrease of density. In the supercritical state, the frequency time correlation function is found to decay with two time scales: One around or less than 100 fs and the other in the region of 250-700 fs. It is found that, for supercritical methanol, the times scales of vibrational spectral diffusion are determined by an interplay between the dynamics of hydrogen bonds, dangling OD groups, and inertial rotation of methanol molecules and the roles of these various components are found to vary with density of the supercritical solvent. Effects of system size on the calculated structural and dynamical properties are also investigated in the present study.

Vibrational dynamics of the water shell of DNA studied by femtosecond two-dimensional infrared spectroscopy

Vibrational dynamics of the water shell around DNA oligomers are addressed by femtosecond two-dimensional (2D) infrared spectroscopy in a wide range of water concentrations. In the 2D spectra, NH stretching excitations of DNA are clearly separated from OH stretching excitations of water. For full hydration, OH stretching excitations display spectral diffusion on a time scale of 500 fs. Vibrational relaxation results in the build-up of a hot water ground state on a 1–2 ps time scale. A comparison of center line slopes of the 2D spectra with the frequency–time correlation function of bulk water suggests a decay of frequency correlations distinctly slower than in bulk H2O. We attribute this behavior to local DNA–water interactions which reduce structural fluctuations and to the smaller rate of resonant OH stretch energy transfer. In contrast, the kinetics of excess energy dissipation are similar in the two systems.

Decelerated Water Dynamics and Vibrational Couplings of Hydrated DNA Mapped by Two-Dimensional Infrared Spectroscopy

Double-stranded DNA oligomers containing 23 alternating adenine-thymine base pairs are studied at different hydration levels by femtosecond two-dimensional (2D) infrared spectrosopy. Coupled NH stretching modes of the A-T pairs and OH stretching excitations of the water shell are discerned in the 2D spectra. Limited changes of NH stretching frequencies and line shapes with increasing hydration suggest spectral dynamics governed by DNA rather than water fluctuations. In contrast, OH stretching excitations of the water shell around fully hydrated DNA undergo spectral diffusion on a ~500 fs time scale. The center line slopes of the 2D spectra of hydrated DNA demonstrate a slower decay of the frequency-time correlation function (TCF) than that in neat water, as is evident from a comparison with 2D spectra of neat H(2)O and theoretical TCFs. We attribute this behavior to reduced structural fluctuations of the water shell and a reduced rate of resonant OH stretching energy transfer.

An ab initio molecular dynamics study of diffusion, orientational relaxation and hydrogen bond dynamics in acetone–water mixtures

A theoretical study of the dynamics of water–acetone mixtures is carried out by using the methods of ab initio molecular dynamics for trajectory generation, time series analysis for frequency calculations and time correlation function approach for calculations of various dynamical quantities. It is found that diffusion coefficients and orientational relaxation times of water and acetone molecules change in a nonlinear manner with variation of composition of the mixture. The lifetimes of acetone–water hydrogen bonds are found to be shorter than that of water–water hydrogen bonds and both are found to increase with decrease of water concentration. The vibrational spectral diffusion of OD stretch modes of deuterated water molecules is also investigated for the equimolar mixture of water and acetone and the results are correlated with the dynamics of water–water and water–acetone hydrogen bonds and also of dangling OD modes.