Dynamics of water confined in reversed micelles: multidimensional vibrational spectroscopy study.

Here we perform a comprehensive study of ultrafast molecular and vibrational dynamics of water confined in small reversed micelles (RMs). The molecular picture is elucidated with two-dimensional infrared (2D IR) spectroscopy of water OH stretch vibrations and molecular dynamics simulations, bridged by theoretical calculations of linear and 2D IR vibrational spectra. To investigate the effects of intermolecular coupling, experiments and modeling are performed for isotopically diluted (HDO in D2O) and undiluted (H2O) water. We put a separation of water inside RMs into two subensembles (water-bound and surfactant-bound molecules), observed by many before, on a solid theoretical basis. Water molecules fully attached to the lipid interface ("shell" water) are decoupled from one another and from the central water nanopool ("core" water). The environmental fluctuations are largely "frozen" for the shell water, while the core waters demonstrate much faster dynamics but still not as fast as in the bulk case. A substantial nanoconfinement effect on the dynamics of the core water is observed after disentanglement of the shell water contribution, which is fully confirmed by the simulations of 2D IR spectra. Current results provide new insights into interaction between biological objects like membranes or proteins with the surrounding aqueous bath, and highlight peculiarities in vibrational energy redistribution near the lipid surface.

Dissimilar dynamics of coupled water vibrations.

Dissimilar dynamics of coupled stretch vibrations of a water molecule are revealed by two-dimensional IR correlation spectroscopy. These are caused by essentially non-Gaussian fluctuations of the electric field exerted by the environment on the individual OH stretch vibrations. Non-Gaussian statistics of the individual site frequency fluctuations results in distinctively different dephasing of the symmetric and asymmetric eigenmodes. This phenomenon can only be described if the assumption of Gaussian dynamics in the traditional theories is abandoned.

Ultrafast energy transfer in water-AOT reverse micelles.

A spectroscopic investigation of the vibrational dynamics of water in a geometrically confined environment is presented. Reverse micelles of the ternary microemulsion H2O/AOT/n-octane (AOT = bis-2-ethylhexyl sulfosuccinate or aerosol-OT) with diameters ranging from 1 to 10 nm are used as a model system for nanoscopic water droplets surrounded by a soft-matter boundary. Femtosecond nonlinear infrared spectroscopy in the OH-stretching region of H2O fully confirms the core/shell model, in which the entrapped water molecules partition onto two molecular subensembles: a bulk-like water core and a hydration layer near the ionic surfactant headgroups. These two distinct water species display different relaxation kinetics, as they do not exchange vibrational energy. The observed spectrotemporal ultrafast response exhibits a local character, indicating that the spatial confinement influences approximately one molecular layer located near the water-amphiphile boundary. The core of the encapsulated water droplet is similar in its spectroscopic properties to the bulk phase of liquid water, i.e., it does not display any true confinement effects such as droplet-size-dependent vibrational lifetimes or rotational correlation times. Unlike in bulk water, no intermolecular transfer of OH-stretching quanta occurs among the interfacial water molecules or from the hydration shell to the bulk-like core, indicating that the hydrogen bond network near the H2O/AOT interface is strongly disrupted.

Ultrafast anisotropy dynamics of water molecules dissolved in acetonitrile.

Infrared pump-probe experiments are performed on isolated H(2)O molecules diluted in acetonitrile in the spectral region of the OH stretching vibration. The large separation between water molecules excludes intermolecular interactions, while acetonitrile as a solvent provides substantial hydrogen bonding. Intramolecular coupling between symmetric and asymmetric modes results in the anisotropy decay to the frequency-dependent values of approximately 0-0.2 with a 0.2 ps time constant. The experimental data are consistent with a theoretical model that includes intramolecular coupling, anharmonicity, and environmental fluctuations. Our results demonstrate that intramolecular processes are essential for the H(2)O stretching mode relaxation and therefore can compete with the intermolecular energy transfer in bulk water.