Effects of dispersion interactions on the structure, polarity, and dynamics of liquid-vapor interface of an aqueous NaCl solution: Results of first principles simulations at room temperature

Abstract

The effects of dispersion interaction on the structure, polarity, and dynamics of liquid-vapor interface of a concentrated (5.3M) aqueous NaCl solution have been investigated through first-principles simulations. Among the structural properties, we have investigated the inhomogeneous density profiles of molecules, hydrogen bond distributions, and orientational profiles. On the dynamical side, we have calculated diffusion, orientational relaxation, hydrogen bond dynamics, and vibrational spectral diffusion of molecules. The polarity of water molecules across the interface is also calculated. Our simulation results are compared with those when no dispersion corrections are included. It is found that the inclusion of dispersion correction predicts an overall improvement of the structural properties of liquid water. The current study reveals a faster relaxation of hydrogen bonds, diffusion, and rotational motion for both interfacial and bulk molecules compared to the results when no such dispersion corrections are included. The dynamics of vibrational frequency fluctuations are also calculated which capture the relaxation of hydrogen bond fluctuations in the bulk and interfacial regions. Generally, the hydrogen bonds at the interfaces are found to have longer lifetimes due to reduced cooperative effects