Water dynamics in small reverse micelles in two solvents: two-dimensional infrared vibrational echoes with two-dimensional background subtraction

Water dynamics as reflected by the spectral diffusion of the water hydroxyl stretch were measured in w(0) = 2 (1.7 nm diameter) Aerosol-OT (AOT)/water reverse micelles in carbon tetrachloride and in isooctane solvents using ultrafast 2D IR vibrational echo spectroscopy. Orientational relaxation and population relaxation are observed for w(0) = 2, 4, and 7.5 in both solvents using IR pump-probe measurements. It is found that the pump-probe observables are sensitive to w(0), but not to the solvent. However, initial analysis of the vibrational echo data from the water nanopool in the reverse micelles in the isooctane solvent seems to yield different dynamics than the CCl(4) system in spite of the fact that the spectra, vibrational lifetimes, and orientational relaxation are the same in the two systems. It is found that there are beat patterns in the interferograms with isooctane as the solvent. The beats are observed from a signal generated by the AOT/isooctane system even when there is no water in the system. A beat subtraction data processing procedure does a reasonable job of removing the distortions in the isooctane data, showing that the reverse micelle dynamics are the same within experimental error regardless of whether isooctane or carbon tetrachloride is used as the organic phase. Two time scales are observed in the vibrational echo data, ~1 and ~10 ps. The slower component contains a significant amount of the total inhomogeneous broadening. Physical arguments indicate that there is a much slower component of spectral diffusion that is too slow to observe within the experimental window, which is limited by the OD stretch vibrational lifetime.     

Testing the core/shell model of nanoconfined water in reverse micelles using linear and nonlinear IR spectroscopy

A core/shell model has often been used to describe water confined to the interior of reverse micelles. The validity of this model for water encapsulated in AOT/isooctane reverse micelles ranging in diameter from 1.7 to 28 nm (w0 = 2-60) and bulk water is investigated using four experimental observables: the hydroxyl stretch absorption spectra, vibrational population relaxation times, orientational relaxation rates, and spectral diffusion dynamics. The time dependent observables are measured with ultrafast infrared spectrally resolved pump-probe and vibrational echo spectroscopies. Major progressive changes appear in all observables as the system moves from bulk water to the smallest water nanopool, w0 = 2. The dynamics are readily distinguishable for reverse micelle sizes smaller than 7 nm in diameter (w0 = 20) compared to the response of bulk water. The results also demonstrate that the size dependent absorption spectra and population relaxation times can be quantitatively predicted using a core-shell model in which the properties of the core (interior of the nanopool) are taken to be those of bulk water and the properties of the shell (water associated with the headgroups) are taken to be those of w0 = 2. A weighted sum of the core and shell components reproduces the size dependent spectra and the nonexponential population relaxation dynamics. However, the same model does not reproduce the spectral diffusion and the orientational relaxation experiments. It is proposed that, when hydrogen bond structural rearrangement is involved (orientational relaxation and spectral diffusion), dynamical coupling between the shell and the core cause the water nanopool to display more homogeneous dynamics. Therefore, the absorption spectra and vibrational lifetime decays can discern different hydrogen bonding environments whereas orientational and spectral diffusion correlation functions predict that the dynamics are size dependent but not as strongly spatially dependent within a reverse micelle.     

Solute rotational dynamics at the water liquid/vapor interface

The rotational dynamics of a number of diatomic molecules adsorbed at different locations at the interface between water and its own vapors are studied using classical molecular dynamics computer simulations. Both equilibrium orientational and energy correlations and nonequilibrium orientational and energy relaxation correlations are calculated. By varying the dipole moment of the molecule and its location, and by comparing the results with those in bulk water, the effects of dielectric and mechanical frictions on reorientation dynamics and on rotational energy relaxation can be studied. It is shown that for nonpolar and weekly polar solutes, the equilibrium orientational relaxation is much slower in the bulk than at the interface. As the solute becomes more polar, the rotation slows down and the surface and bulk dynamics become similar. The energy relaxation (both equilibrium and nonequilibrium) has the opposite trend with the solute dipole (larger dipoles relax faster), but here again the bulk and surface results converge as the solute dipole is increased. It is shown that these behaviors correlate with the peak value of the solvent-solute radial distribution function, which demonstrates the importance of the first hydration shell structure in determining the rotational dynamics and dependence of these dynamics on the solute dipole and location.     

Photophysics and locations of IR125 and C152 in AOT reverse micelles

Many fluorescent chromophores have been employed to investigate the nature and dynamics of the water confined in reverse micelles (RMs). However, some questions remain as to the location of a probe in a RM and the diameter of the RM at which the physical characteristic of the water inside RMs becomes similar to that of bulk water. In this work, we systematically studied the photophysics of IR125 and C152 in AOT RMs at different w(0) by means of static absorption and fluorescence spectroscopy as well as time-resolved fluorescence spectroscopy. We obtained the absorption maxima, fluorescence emission maxima, fluorescence lifetime, and reorientation time of IR125 and C152 in AOT RMs at corresponding w(0). We found that all obtained photophysical parameters of IR125 and C152 in AOT RMs as a function of w(0) have a distinct changeover point around w(0) = 8, indicating that there is a dramatic change in the nature of the water confined in AOT RMs around w(0) = 8. The observed changeover point around w(0) = 8 is well in agreement with the Satpati's report (ChemPhysChem, 2009, 10, 2966). In addition, we observed that the measured reorientation time of IR125 in AOT RMs increases with the increase of w(0), which is opposite to the trend of change in the measured reorientation time of C152 in AOT RMs with the increase of w(0). We found that IR125 prefers to reside in the water pool of AOT RMs and that C152 prefers to reside in the outer side of the interfacial region or the nonpolar n-heptane phase of AOT RMs. Furthermore, we found that the time-resolved fluorescence anisotropy of IR125 in smaller w(0) AOT RMs primarily measures the reorientation of RMs and the time-resolved fluorescence anisotropy of IR125 in larger w(0) AOT RMs measures the reorientation of IR125 in the water pool confined in RMs. This work demonstrated that IR125 is an excellent probe to study the nature and dynamics of the water confined in AOT RMs.     

Water dynamics--the effects of ions and nanoconfinement

Hydrogen bond dynamics of water in highly concentrated NaBr salt solutions and reverse micelles are studied using ultrafast 2D-IR vibrational echo spectroscopy and polarization-selective IR pump-probe experiments performed on the OD hydroxyl stretch of dilute HOD in H(2)O. The vibrational echo experiments measure spectral diffusion, and the pump-probe experiments measure orientational relaxation. Both experimental observables are directly related to the structural dynamics of water's hydrogen bond network. The measurements performed on NaBr solutions as a function of concentration show that the hydrogen bond dynamics slow as the NaBr concentration increases. The most pronounced change is in the longest time scale dynamics which are related to the global rearrangement of the hydrogen bond structure. Complete hydrogen bond network randomization slows by a factor of approximately 3 in approximately 6 M NaBr solution compared to that in bulk water. The hydrogen bond dynamics of water in nanoscopically confined environments are studied by encapsulating water molecules in ionic head group (AOT) and nonionic head group (Igepal CO 520) reverse micelles. Water dynamics in the nanopools of AOT reverse micelles are studied as a function of size by observing orientational relaxation. Orientational relaxation dynamics deviate significantly from bulk water when the size of the reverse micelles is smaller than several nm and become nonexponential and slower as the size of the reverse micelles decreases. In the smallest reverse micelles, orientational relaxation (hydrogen bond structural randomization) is almost 20 times slower than that in bulk water. To determine if the changes in dynamics from bulk water are caused by the influence of the ionic head groups of AOT or the nanoconfinement, the water dynamics in 4 nm nanopools in AOT reverse micelles (ionic) and Igepal reverse micelles (nonionic) are compared. It is found that the water orientational relaxation in the 4 nm diameter nanopools of the two types of reverse micelles is almost identical, which indicates that confinement by an interface to form a nanoscopic water pool is a primary factor governing the dynamics of nanoscopic water rather than the presence of charged groups at the interface.     

Inhibited phenol ionization in reverse micelles: confinement effect at the nanometer scale

We found that the absorption spectra of 2-acetylphenol (2-HAP), 4-acetylphenol (4-HAP), and p-nitrophenol (p-NPh) in water/sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane reverse micelles (RMs) at various W(0) (W(0) = [H(2)O]/[surfactant]) values studied changed with time if (-)OH ions were present in the RM water pool. There is an evolution of ionized phenol (phenolate) bands to nonionized phenol absorption bands with time and this process is faster at low W(0) values and with phenols with higher bulk water pK(a) values. That is, in bulk water and at the hydroxide anion concentration used, only phenolate species are observed, whereas in AOT RMs at this fixed hydroxide anion concentration, ionized phenols convert into nonionized phenol species over time. Furthermore, we demonstrate that, independent of the (-)OH concentration used to prepare the AOT RMs, the nonionized phenols are the more stable species in the RM media. We explain our results by considering that strong hydrogen-bonding interactions between phenols and the AOT polar head groups result in the existence of only nonionized phenols at the AOT RM interface. The situation is quite different when the phenols are dissolved in cationic benzyl-n-hexadecyldimethylammonium chloride RMs. Therein, only phenolates species are present at the (-)OH concentrations used. The results clearly demonstrate that the classical definition of pH does not apply in a confined environment, such as in the interior of RMs and challenge the general idea that pH can be determined inside RMs.     

Ion pairs of crystal violet in sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles

The interfacial localization and the ion pair formation of the positively charged dye crystal violet (CV) in sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles (AOT RMs) were studied by several structural and spectroscopic techniques and by quantum chemical calculations. The size and shape of the AOT RMs in the presence of CV were investigated by small-angle X-ray scattering, showing that CV does not significantly change the RM structure. CV localization as a function of the water to surfactant molar ratio (w(0)) was characterized by H(1) and (13)C NMR, indicating the close proximity of CV to the sulfosuccinate group of AOT at small and large w(0) values. These results were confirmed by calculation of magnetic shielding constants using the gauge-independent atomic orbital method with the HF/6-31G(d) basis set. Two different types of ion pairs between AOT and CV, i.e., contact ion pair (CIPs) and solvent-separated ion pair (SSIPs), were characterized by UV-vis spectroscopy and quantum chemical calculations using the semiempirical ZINDO-CI method. In nonpolar isotropic solvents CIPs are formed with an association constant (K(ASSOC)) of 2 x 10(4) mol(-1) L in isooctane and 750 mol(-1) L in chloroform. In AOT RMs at low w(0), CV-AOT CIPs are also formed. By increasing w(0), there is a sharp decrease in the CIP association free energy, and SSIPs are formed. (CV(+))(H(2)O)(AOT(-)) SSIPs are stable in the AOT RM up to the largest w(0) tested (w(0) = 33).     

Water motion in reverse micelles studied by quasielastic neutron scattering and molecular dynamics simulations

Motion of water molecules in Aerosol OT [sodium bis(2-ethylhexyl) sulfosuccinate, AOT] reverse micelles with water content w(0) ranging from 1 to 5 has been explored both experimentally through quasielastic neutron scattering (QENS) and with molecular dynamics (MD) simulations. The experiments were performed at the energy resolution of 85 microeV over the momentum transfer (Q) range of 0.36-2.53 A(-1) on samples in which the nonpolar phase (isooctane) and the AOT alkyl chains were deuterated, thereby suppressing their contribution to the QENS signal. QENS results were analyzed via a jump-diffusion/isotropic rotation model, which fits the results reasonably well despite the fact that confinement effects are not explicitly taken into account. This analysis indicates that in reverse micelles with low-water content (w(0)=1 and 2.5) translational diffusion rate is too slow to be detected, while for w(0)=5 the diffusion coefficient is much smaller than for bulk water. Rotational diffusion coefficients obtained from this analysis increase with w(0) and are smaller than for bulk water, but rotational mobility is less drastically reduced than translational mobility. Using the Faeder/Ladanyi model [J. Phys. Chem. B 104, 1033 (2000)] of reverse micelle interior, MD simulations were performed to calculate the self-intermediate scattering function F(S)(Q,t) for water hydrogens. Comparison of the time Fourier transform of this F(S)(Q,t) with the QENS dynamic structure factor S(Q,omega), shows good agreement between the model and experiment. Separate intermediate scattering functions F(S) (R)(Q,t) and F(S) (CM)(Q,t) were determined for rotational and translational motion. Consistent with the decoupling approximation used in the analysis of QENS data, the product of F(S) (R)(Q,t) and F(S) (CM)(Q,t) is a good approximation to the total F(S)(Q,t). We find that the decay of F(S) (CM)(Q,t) is nonexponential and our analysis of the MD data indicates that this behavior is due to lower water mobility close to the interface and to confinement-induced restrictions on the range of translational displacements. Rotational relaxation also exhibits nonexponential decay. However, rotational mobility of O-H bond vectors in the interfacial region remains fairly high due to the lower density of water-water hydrogen bonds in the vicinity of the interface.     

Spectrometric study of AOT-hydrolysis reaction in water/AOT/isooctane microemulsions using phenolphthalein as a chemical probe

The kinetics of the alkaline hydrolysis of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in water/AOT/isooctane microemulsions has been studied by monitoring the absorbance change of the phenolphthalein in the system with time. The apparent first-order rate constant k(obs) has been obtained and found to be dependent on both the molar ratio of water to AOT ω and the temperature. The dependences of k(obs) on ω have been analyzed by a pseudophase model which gives the true rate constants k(i) of the AOT-hydrolysis reaction on the interface and the partition coefficients K(wi) for the distribution of OH(-) between aqueous and interface pseudophases at various temperatures; the latter is almost independent of the temperature and ω. The temperature dependences of the reaction rate constants k(obs) and k(i) have been analyzed to obtain enthalpy ΔH(≠), entropy ΔS(≠), and energy E(a) of activation, which indicate that the distribution of OH(-) between aqueous and interface pseudophases increases ΔS(≠) but makes no contribution to E(a) and ΔH(≠). The influence of the overall concentration of AOT in the system on the rate constant has been examined and found to be negligible. It contradicts with what was reported by García-Río et al. (1) but confirms that the first-order reaction of the AOT-hydrolysis takes place on the surfactant interface. The study of the influence of AOT-hydrolysis on the kinetics of the alkaline fading of crystal violet or phenolphthalein in the water/AOT/isooctane microemulsions suggests that corrections for the AOT-hydrolysis in these reactions are required.     

Reverse micellar aggregates: effect on ketone reduction. 2. Surfactant role

Kinetics of the reduction of 3-chloroacetophenone (CAF) with sodium borohydride (NaBH(4)) were followed by UV-vis spectroscopy at 27.0 degrees C in different reverse micellar media, toluene/BHDC/water and toluene/AOT/water, and compared with results in an isooctane/AOT/water reverse micellar system. AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate, and BHDC is benzyl-n-hexadecyl dimethylammonium chloride. The kinetic profiles were investigated as a function of variables such as surfactant and NaBH(4) concentration and the amount of water dispersed in the reverse micelles, W(0) = [H(2)O]/[surfactant]. In all cases, the first-order rate constant, k(obs), increases with the concentration of surfactant as a consequence of incorporating the substrate into the interface of the reverse micelles where the reaction takes place. The reaction is faster at the cationic interface than at the anionic one probably because the negative ion BH(4)(-) is part of the cationic interface. The effect of the external solvent on the reaction shows that reduction is favored in the isooctane/AOT/water reverse micellar system than that with an aromatic solvent. This is probably due to BH(4)(-) being more in the water pool of the toluene/AOT/water reverse micellar system. The kinetic profile upon water addition depends largely on the type of interface. In the BHDC system, k(obs) increases with W(0) in the whole range studied while in AOT the kinetic profile has a maximum at W(0) approximately 5, probably reflecting the fact that BH(4)(-) is part of the cationic interface while, in the anionic one, there is a strong interaction between water and the polar headgroup of AOT below W(0) = 5 and, above that, BH(4)(-) is repelled from the interface once the water pool has formed. Application of a kinetic model based on the pseudophase formalism, which considers the distribution of the ketone between the continuous medium and the interface and assumes that reaction takes place only at the interface, has enabled us to estimate rate constants at the interface of the reverse micellar systems. At W(0) < 10, it was considered that NaBH(4) is wholly at the interface and, at W(0) >/= 10, where there are free water molecules, also the partitioning between the interface and the water pool was taken into account. The results were used to evaluate CAF and NaBH(4) distribution constants between the different pseudophases as well as the second-order reaction rate constant of the reduction reaction in the micellar interface.     

The effect of different polymer length on water droplets of reverse AOT microemulsion

We study the effect of polyethylene glycol (PEG) on the dynamic and structure of water droplets at the reverse sodium bis-(2-ethylhexyl) sulfosuccinate (AOT) microemulsion. The mixture of water and oil with anionic surfactant AOT can form microemulsion. The dynamic of microemulsion in the presence of PEG is investigated by photon correlation spectroscopy technique. We mainly focus on the variation of the translational diffusion behaviour as a function of the polymer concentration and polymer length scale. By increasing the content of the lowest PEG length scale (M_n = 285), the dynamic of microemulsion slows down. In addition, one relaxation process is distinguished for all polymer concentration. However, for the two higher polymer length scale (M_n = 2200 and 6000), two relaxations are observed and the dynamic of microemulsion speeds up. We used the small angle X-ray scattering technique to monitor the size and the polydispersity of the mixture system (AOT microemulsion/PEG).     

Effect of the Cationic Surfactant Moiety on the Structure of Water Entrapped in Two Catanionic Reverse Micelles Created from Ionic Liquid‐Like Surfactants

The behavior of water entrapped in reverse micelles (RMs) formed by two catanionic ionic liquid‐like surfactants, benzyl‐n‐hexadecyldimethylammonium 1,4‐bis‐2‐ethylhexylsulfosuccinate (AOT‐BHD) and cetyltrimethylammonium 1,4‐bis‐2‐ethylhexylsulfosuccinate (AOT‐CTA), was investigated by using dynamic (DLS) and static (SLS) light scattering, FTIR, and ¹H NMR spectroscopy techniques. To the best of our knowledge, this is the first report in which AOT‐CTA has been used to create RMs and encapsulate water. DLS and SLS results revealed the formation of RMs in benzene and the interaction of water with the RM interface. From FTIR and ¹H NMR spectroscopy data, a difference in the magnitude of the water–catanionic surfactant interaction at the interface is observed. For the AOT‐BHD RMs, a strong water–surfactant interaction can be invoked whereas for AOT‐CTA this interaction seems to be weaker. Consequently, more water molecules interact with the interface in AOT‐BHD RMs with a completely disrupted hydrogen‐bond network, than in AOT‐CTA RMs in which the water structure is partially preserved. We suggest that the benzyl group present in the BHD⁺ moiety in AOT‐BHD is responsible for the behavior of the catanionic interface in comparison with the interface created in AOT‐CTA. These results show that a simple change in the cationic component in the catanionic surfactant promotes remarkable changes in the RMs interface with interesting consequences, in particular when using the systems as nanoreactors.     

Proton transport and the water environment in nafion fuel cell membranes and AOT reverse micelles

The properties of confined water and diffusive proton-transfer kinetics in the nanoscopic water channels of Nafion fuel cell membranes at various hydration levels are compared to water in a series of well-characterized AOT reverse micelles with known water nanopool sizes using the photoacid pyranine as a molecular probe. The side chains of Nafion are terminated by sulfonate groups with sodium counterions that are arrayed along the water channels. AOT has sulfonate head groups with sodium counterions that form the interface with the reverse micelle's water nanopool. The extent of excited-state deprotonation is observed by steady-state fluorescence measurements. Proton-transfer kinetics and orientational relaxation are measured by time-dependent fluorescence using time-correlated single photon counting. The time dependence of deprotonation is related to diffusive proton transport away from the photoacid. The fluorescence reflecting the long time scale proton transport has an approximately t-0.8 power law decay in contrast to bulk water, which has a t-3/2 power law. For a given hydration level of Nafion, the excited-state proton transfer and the orientational relaxation are similar to those observed for a related size AOT water nanopool. The effective size of the Nafion water channels at various hydration levels are estimated by the known size of the AOT reverse micelles that display the corresponding proton-transfer kinetics and orientational relaxation.     

Reverse micellar aggregates: effect on ketone reduction. 1. Substrate role

The reduction of three aromatic ketones, acetophenone (AF), 4-methoxyacetophenone (MAF), and 3-chloroacetophenone (CAF), by NaBH(4) was followed by UV-vis spectroscopy in reverse micellar systems of water/AOT/isooctane at 25.0 degrees C (AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate). The first-order rate constants, k(obs), increase with the concentration of surfactant due to the substrate incorporation at the reverse micelle interface, where the reaction occurs. For all the ketones the reactivity is lower at the micellar interface than in water, probably reflecting the low affinity of the anionic interface for BH(4)(-). Kinetic profiles upon water addition show maxima in k(obs) at W(0) approximately 5 probably reflecting a strong interaction between water and the ionic headgroup of AOT; at W(0) < 5 by increasing W(0) BH(4)(-) is repelled from the anionic interface once the water pool forms. The order of reactivity was CAF > AF > MAF. Application of a kinetic model based on the pseudophase formalism, which considers distribution of the ketones between the continuous medium and the interface, and assumes that reaction take place only at the interface, gives values of the rate constants at the interface of the reverse micellar system. At W(0) = 5, we conclude that NaBH(4) is wholly at the interface, and at W(0) = 10 and 15, where there are free water molecules, the partitioning between the interface and the water pool has to be considered. The results were used to estimate the ketone and borohydride distribution constants between the different pseudophases as well as the second-order reaction rate constant at the micellar interface.     

Effect of AOT on enzymatic activity of the organic solvent resistant tyrosinase from Streptomyces sp. REN-21 in aqueous solutions and water-in-oil microemulsions

The effect of AOT (sodium-bis(2-ethylhexyl sulfosuccinate)) on enzymatic activity of the organic solvent resistant tyrosinase (OSRT) in aqueous phosphate buffer solutions and in water-in-oil microemulsions of the water/AOT/isooctane system has been investigated. In contrast to mushroom tyrosinase, AOT does not activate OSRT in aqueous solutions, altering its activity very little at concentrations lower than 2 mM. Increasing contents of AOT in isooctane reduce the observed initial reaction rates of oxidation of t-butylcatechol (tBC) and 4-methylcatechol (4-MC). Similarly to mushroom tyrosinase, the effect has been described using an equation based on preferential binding of the substrates by surfactant interface layers. The apparent Michaelis-Menten substrate binding constants increase linearly with AOT concentration (with slopes of 0.12+/-0.02 and 0.051+/-0.006 for tBC and 4-MC, respectively), and the effective enzyme turnover number in the microemulsions remains practically constant.     

Molecular dynamics study of the liquid-vapor interface of acetonitrile: equilibrium and dynamical properties

The equilibrium and dynamical properties of the liquid-vapor interface of pure acetonitrile are studied by means of molecular dynamics simulations. Both nonpolarizable and polarizable models are employed in the present study. For the nonpolarizable model, the simulations are carried out for two different system sizes and at two different temperatures whereas the simulation with the polarizable model is done for a single system. The inhomogeneous density, anisotropic orientational profile, the width of the interface, and also the surface tension are calculated at room temperature and also at a lower temperature of 273 K. The dynamical aspects of the interface are investigated in terms of the single-particle dynamical properties such as the relaxation of velocity autocorrelation and the translational diffusion coefficients along the perpendicular and parallel directions and the dipole orientational relaxation of the interfacial acetonitrile molecules. The results of the interfacial dynamics are compared with those of the corresponding bulk phases at both temperatures. The convergence of the calculated results with respect to the length of simulation runs and the system size are also discussed.     

On the Formation of Water/Oil-Microemulsions

The formation of a so-called water/oil (W/O)-microemulsion (AOT/isooctane/water) was followed by light scattering and ultracentrifuge measurements. With increasing weighed-in water concentrations the microemulsion is stabilized by repeated aggregational processes of micelles containing water due to a decrease of the free interfacial enthalpy. This process conforms very satisfactorily to a model describing an adsorption of surfactants at the water/hydrocarbon interface resulting from dipole-image dipole interactions.     

Polarization and experimental configuration analyses of sum frequency generation vibrational spectra, structure, and orientational motion of the air/water interface

Here we report a detailed study on spectroscopy, structure, and orientational distribution, as well as orientational motion, of water molecules at the air/water interface, investigated with sum frequency generation vibrational spectroscopy (SFG-VS). Quantitative polarization and experimental configuration analyses of the SFG data in different polarizations with four sets of experimental configurations can shed new light on our present understanding of the air/water interface. Firstly, we concluded that the orientational motion of the interfacial water molecules can only be in a limited angular range, instead of rapidly varying over a broad angular range in the vibrational relaxation time as suggested previously. Secondly, because different vibrational modes of different molecular species at the interface has different symmetry properties, polarization and symmetry analyses of the SFG-VS spectral features can help the assignment of the SFG-VS spectra peaks to different interfacial species. These analyses concluded that the narrow 3693 cm(-1) and broad 3550 cm(-1) peaks belong to C(infinityv) symmetry, while the broad 3250 and 3450 cm(-1) peaks belong to the symmetric stretching modes with C2v symmetry. Thus, the 3693 cm(-1) peak is assigned to the free OH, the 3550 cm(-1) peak is assigned to the singly hydrogen-bonded OH stretching mode, and the 3250 and 3450 cm(-1) peaks are assigned to interfacial water molecules as two hydrogen donors for hydrogen bonding (with C2v symmetry), respectively. Thirdly, analysis of the SFG-VS spectra concluded that the singly hydrogen-bonded water molecules at the air/water interface have their dipole vector directed almost parallel to the interface and is with a very narrow orientational distribution. The doubly hydrogen-bonded donor water molecules have their dipole vector pointing away from the liquid phase.     

Orientational dynamics of water confined on a nanometer length scale in reverse micelles

The time-resolved orientational anisotropies of the OD hydroxyl stretch of dilute HOD in H(2)O confined on a nanometer length scale in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles are studied using ultrafast infrared polarization and spectrally resolved pump-probe spectroscopy, and the results are compared to the same experiments on bulk water. The orientational anisotropy data for three water nanopool sizes (4.0, 2.4, and 1.7 nm) can be fitted well with biexponential decays. The biexponential decays are analyzed using a wobbling-in-a-cone model that involves fast orientational diffusion within a cone followed by slower, full orientational relaxation. The data provide the cone angles, the diffusion constants for motion within the cones, and the final diffusion constants as a function of the nanopool size. The two processes can be interpreted as a local angular fluctuation of the OD and a global hydrogen bond network rearrangement process. The trend in the relative amplitudes of the long and short exponential decays suggest an increasing rigidity as the nanopool size decreases. The trend in the long decay constants indicates a longer hydrogen bond network rearrangement time with decreasing reverse micelle size. The anisotropy measurements for the reverse micelles studied extrapolate to approximately 0.33 rather than the ideal value of 0.4, suggesting the presence of an initial inertial component in the anisotropy decay that is too fast to resolve. The very fast decay component is consistent with initial inertial orientational motion that is seen in published molecular-dynamics simulations of water in AOT reverse micelles. The angle over which the inertial orientational motion occurs is determined. The results are in semiquantitative agreement with the molecular-dynamics simulations.     

Entropy and dynamics of water in hydration layers of a bilayer

We compute the entropy and transport properties of water in the hydration layer of dipalmitoylphosphatidylcholine bilayer by using a recently developed theoretical scheme [two-phase thermodynamic model, termed as 2PT method; S.-T. Lin et al., J. Chem. Phys. 119, 11792 (2003)] based on the translational and rotational velocity autocorrelation functions and their power spectra. The weights of translational and rotational power spectra shift from higher to lower frequency as one goes from the bilayer interface to the bulk. Water molecules near the bilayer head groups have substantially lower entropy (48.36 J/mol/K) than water molecules in the intermediate region (51.36 J/mol/K), which have again lower entropy than the molecules (60.52 J/mol/K) in bulk. Thus, the entropic contribution to the free energy change (TΔS) of transferring an interface water molecule to the bulk is 3.65 kJ/mol and of transferring intermediate water to the bulk is 2.75 kJ/mol at 300 K, which is to be compared with 6.03 kJ/mol for melting of ice at 273 K. The translational diffusion of water in the vicinity of the head groups is found to be in a subdiffusive regime and the rotational diffusion constant increases going away from the interface. This behavior is supported by the slower reorientational relaxation of the dipole vector and OH bond vector of interfacial water. The ratio of reorientational relaxation time for Legendre polynomials of order 1 and 2 is approximately 2 for interface, intermediate, and bulk water, indicating the presence of jump dynamics in these water molecules.