Theoretical Study of the Two-Dimensional Vibrational Sum Frequency Generation Spectroscopy of the Air-Water Interface at Varying Temperature and Its Connections to the Interfacial Structure and Dynamics.

We performed a theoretical study of the temperature variation of two-dimensional vibrational sum frequency generation (2D-VSFG) spectra of the OH stretch modes at air-water interfaces in the mid-IR region. The calculations are performed at four different temperatures from 250 to 325 K by using a combination of techniques involving response function formalism of nonlinear spectroscopy, electronic structure calculations, and molecular dynamics simulations. Also, the calculations are performed for isotopically dilute solutions so that the intra- and intermolecular coupling between the vibrational modes of interest can be ignored. We have established the connections of temperature variation of various frequency- and time-dependent features of the calculated spectra to the changes in the underlying structure and dynamics of the interfaces. The results reveal that interfacial water is dynamically more heterogeneous than bulk water, with three dominant dynamical processes exhibiting their corresponding time-dependent features in the 2D-VSFG spectrum. These are the spectral diffusion of hydrogen-bonded OH groups at the interface, conversion of an initially hydrogen-bonded OH group to a dangling OH which is a stable state for surface water, unlike the bulk water, and the third one, which involves the conversion of an initially free or dangling OH group to its hydrogen-bonded state at the interface. The temporal appearance of the cross peaks corresponding to interconversion of the hydrogen-bonded state to the dangling state or vice versa of an interfacial OH group is found to take place at a slower rate than the dynamics of spectral diffusion of hydrogen-bonded molecules at the interface, which, in turn, is slower than the corresponding spectral diffusion of bulk water molecules. The temperature variation of these dynamic processes can be linked to the decay of appropriate hydrogen-bond and non-hydrogen-bond time correlation functions of interfacial water molecules for the different air-water systems studied in this work.

Dynamical Crossover of Interfacial Water upon Melting of a Lipid Bilayer: Influence of Different Parts of the Headgroups.

All-atom molecular dynamics simulations of a 1,2-dimyristoyl-sn-glycero-3-phosphocholine bilayer in contact with liquid water were performed at different temperatures ranging from 285 to 320 K. We have investigated the heterogeneity and dynamical transitions in interfacial water as the lipid bilayer undergoes a melting transition. Results are obtained for water at the outer surface of the bilayer and for those buried more deeply in the lipid chains of the bilayer. It is found that lipid bilayer melting influences both the structure and dynamics of interfacial water. The number of interfacial water molecules shows a jump in the melting of the bilayer. The temperature dependence of the diffusivity and orientational relaxation of interfacial water molecules exhibits a dynamical crossover upon melting of the bilayer. The extent of dynamical crossover is found to be rather strong with significant changes in activation barriers for interfacial water around the carbonyl groups, which are deeply buried toward the lipid chains of the bilayer. The dynamical crossover gradually decreases as one moves further away from the outer surface, and it essentially vanishes for water in the region of 5-10 Å from the outer surface. It is found that the lipid melting-induced dynamical crossover of interfacial water is significant only for water that is in close proximity to the bilayer surface or deeply buried into it. The current results reveal that water molecules in different parts of the interface respond differently on melting of the bilayer. The current study also shows that the carbonyl-bound water molecules can play an important role in the phase transition of the bilayer as the temperature is raised through its melting point.

Terahertz Spectrum of Water at Varying Temperatures from 260 to 340 K: Contributions from Permanent and Induced Dipole Correlations at Different Length Scales.

The terahertz (THz) absorption spectrum of water is calculated at varying temperatures from 260 to 340 K from molecular dynamics simulations using a polarizable potential model of water. The current calculations produce the known experimental features of the THz spectrum of water such as the hydrogen-bond stretch mode at ∼200 cm-1 and librational mode at ∼600 cm-1. The peak positions generally show a red shift with an increase of temperature due to the weakening of the hydrogen bonds at higher temperatures. Overall, the changes of the spectrum with temperature are found to be in good agreement with experimental results. The total THz spectrum at a given temperature is dissected into self- and cross-correlation contributions and also into contributions from permanent dipoles, induced dipoles, and permanent-induced dipole correlations. It is shown that while the peak at ∼200 cm-1 due to hydrogen-bond stretching primarily comes from fluctuations of induced dipoles, the librational peak at around 600 cm-1 originates mainly from fluctuations of the permanent dipoles. Also, through calculations of self- and cross-correlations, it is shown that the broad librational peak arises from the superposition of several components like the antisymmetric libration, symmetric libration, and also self-dipole correlations. The length-scale-resolved calculations of cross-correlations reveal the contributions from different solvation shells to the total cross-component of the THz spectrum and how such length-scale-resolved components change with temperature. Results are also presented for the dielectric relaxation of water over different length scales and temperatures.

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.

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.

Deciphering the Properties of Nanoconfined Aqueous Solutions by Vibrational Sum Frequency Generation Spectroscopy.

When confined between walls at nanometer distances, water exhibits surprisingly different properties with reference to bare interfacial water. Based on computer simulations, we demonstrate how vibrational sum frequency generation (VSFG) spectroscopy can be used-even with very mild symmetry breaking-to discriminate multilayer water in wide slit pores from both bilayer and monolayer water confined within molecularly narrow pores. Applying the technique, the VSFG lineshapes of monolayer, bilayer, and multilayer water are found to differ in characteristic ways, which is explained by their distinct density stratifications giving rise to different H-bonding patterns in the respective solvation layers.

Vibrational Sum Frequency Generation Spectra of Water-Vapor Interfaces Covered by Alcohols: Effects of†Surface Coverage and Coupling between Oscillators.

The present study deals with the effects of varying coverage of water surface by alcohols on the vibrational sum frequency generation (VSFG) spectrum of interfacial water. We have considered two different alcohols: Tertiary butyl alcohol (TBA) whose alkyl part is fully branched and stearyl alcohol (STA) which has a long linear alkyl chain with larger hydrophobic surface area than that of TBA. With increase of the alcohol concentration, the hydrogen bonded OH stretch region of the VSFG spectrum is found to change following a regular trend for the STA-water system, whereas non-monotonic variation of the VSFG spectrum is observed for the TBA-water system which can be correlated with the presence of very different interactions of TBA molecules at different concentrations. On increasing the concentration of TBA, the hydrophobic groups get more tilted towards the water phase and significant hydrophobic interactions are introduced at higher concentrations. Whereas, for STA, there is a gradual increase in the hydrophilic interaction. Because of stacking interactions between the long chain alkyl groups, the hydrophobic parts stay outward from the water phase at higher concentrations and a regular change in the VSFG spectrum is observed. We have also presented a computationally efficient scheme to calculate the VSFG spectrum of interfacial systems for coupled oscillators which is expected to be beneficial for the treatment of coupling where the interfacial system size is inherently large.

Effects of stearyl alcohol monolayer on the structure, dynamics and vibrational sum frequency generation spectroscopy of interfacial water.

The structure, dynamics and vibrational spectroscopy of a water surface covered by a monolayer of stearyl alcohol (STA) are investigated by means of molecular dynamics simulations and vibrational sum frequency generation (VSFG) spectral calculations. The STA molecules possess long linear alkyl chains without any branching and have a rather large hydrophobic surface area. The STA-water interface is found to be rather narrow with an ordered outward arrangement of the alcohol chains at the water surface. The water molecules in the interfacial region which contribute most to the observed VSFG spectrum are identified. It is shown that the observed red shift in the hydrogen bonded part of the VSFG spectrum can originate from partial cancellation of the spectral responses from up and down-oriented OH moieties of interfacial water which are hydrogen bonded, respectively, to alcohol and water molecules. The effects of intra and intermolecular coupling to the VSFG spectrum are also calculated for the STA-water interface considered here. On the dynamical side, a slowing down of the hydrogen bond and orientational relaxation is found for the interfacial water. It is found that the ordered arrangement of STA molecules at the surface holds the interfacial water molecules rather tightly and slows down the dynamics. The current results of the STA-water interface are also compared with those of the tertiary butyl alcohol (TBA)-water interface where the alcohol has a fully branched hydrophobic part of the lower surface area.

Ab Initio Molecular Dynamics Study of Aqueous Solutions of Magnesium and Calcium Nitrates: Hydration Shell Structure, Dynamics and Vibrational Echo Spectroscopy.

Ab initio molecular dynamics simulations are performed to study the hydration shell structure, dynamics, and vibrational echo spectroscopy of aqueous Mg(NO3)2 and Ca(NO3)2 solutions. The hydration shell structure is probed through calculations of various ion-ion and ion-water radial and spatial distribution functions. On the dynamical side, calculations have been made for the hydrogen bond dynamics of hydration shells and also residence dynamics and lifetimes of water in different solvation environments. Subsequently, we looked at the dynamics of frequency fluctuations of OD modes of heavy water in different hydration environments. Specifically, the temporal decay of spectral observables of two-dimensional infrared (2DIR) spectroscopy, three pulse echo peak shift (3PEPS) measurements and also of time correlations of frequency fluctuations are calculated to investigate the dynamics of vibrational spectral diffusion of water in different hydration environments in these solutions. The OD stretch frequencies of water molecules in the vicinity of both divalent cations are found to be red-shifted and also fluctuating at a slower rate than other water molecules present in the solutions. The Mg2+ ions are found to be strongly hydrated which can be linked to their lower tendency to form contact ion-pairs and essentially no water exchange between the cationic hydration shells and bulk during the time scale of the current simulations. The stronger hydration of Mg2+ ions make their hydration shells structurally and dynamically more rigid and make the dynamics of hydrogen bonds and vibrational spectral diffusion, as revealed through spectral observables of 2DIR and 3PEPS slower than that for the Ca2+ ions. The structural and spectral dynamics of water molecules outside the cationic solvation shells in the Mg(NO3)2 solution are also found to be relatively slower than that of the Ca(NO3)2 solution and pure water which show the effects of stronger electric fields of Mg2+ ions extending beyond their first hydration shells. Also, water molecules in the hydration shells of the NO3- ions are found to relax at a slower rate in the Mg(NO3)2 solution which manifests the effect countercations have on anionic hydration shells for divalent metal nitrate solutions.

Two-Dimensional Infrared Spectroscopy of Aqueous Solutions of Metal Nitrates: Slowdown of Spectral Diffusion in the Presence of Divalent Cations.

The hydrogen-bonded network of water can be affected both structurally and dynamically by the presence of ions. In the present study, we have considered three aqueous solutions of metal nitrates to investigate the effects of divalent cations (Mg2+ and Ca2+), compared to that of monovalent Na+ ions, on hydrogen-bond fluctuations and vibrational spectral diffusion through calculations of linear and two-dimensional infrared spectra of these solutions at room temperature. We have employed the methods of molecular dynamics simulations using effective polarizable models of ions combined with quantum mechanical calculations of transition variables and statistical mechanical calculations of spectral response functions of vibrational spectroscopy. Divalent cations are found to have much stronger and longer-ranged effects on the structure and dynamics of the hydrogen-bonded network than that induced by the monovalent sodium ions. The blue shifts in the calculated linear spectra are found to follow the Hofmeister trend for the cations. The 2D-IR spectral lineshape and intensity corresponding to three-pulse echo peak shift (3PEPS) experiments are calculated. The timescales of these nonlinear spectral responses and also frequency-time correlations show significant slowing down of spectral diffusion for solutions containing divalent Mg2+ and Ca2+ ions compared to the corresponding dynamics of the solution containing Na+ ions. Unlike NaNO3 solution, the relaxation of frequency and dipole orientational fluctuations of anion-bound water in Mg(NO3)2 and Ca(NO3)2 solutions are found to be somewhat slower than bulk water, which can be attributed to the presence of divalent cations whose effects go beyond their first solvation shells. This is also seen in the dynamics of bulk water in these solutions which is found to be notably slower for the solutions containing divalent cations than that in the NaNO3 solution. Unlike Mg2+ and Ca2+ ions, no specific cationic effect is observed for the Na+ ions.