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.