Analysis of anisotropic local field in sum frequency generation spectroscopy with the charge response kernel water model

A new flexible and polarizable water model based on the charge response kernel (CRK) theory is developed for the analysis of sum frequency generation (SFG) spectroscopy. The CRK model well describes several bulk water properties and SFG spectrum by molecular dynamics (MD) calculations. While the flexible and polarizable MD simulation generally adopts the short-range damping of intermolecular interaction, it is found that the same procedure is not adequate for the calculation of transition dipole in strongly hydrogen bonding environment. Accordingly, the improved calculation of the nonlinear susceptibility of water surface results in the positive imaginary part in the 3000-3200 cm(-1) region, which is consistent with recent phase-sensitive experiments. The mechanism of the positive region is attributed to the anisotropic local field effect induced by the orientational correlation of surface water.