Microscopic structure and dynamics of air/water interface by computer simulations--comparison with sum-frequency generation experiments.

The air/water interface was simulated and the mode amplitudes and their ratios of the effective nonlinear sum-frequency generation (SFG) susceptibilities (A(eff)'s) were calculated for the ssp, ppp, and sps polarization combinations and compared with experiments. By designating "surface-sensitive" free OH bonds on the water surface, many aspects of the SFG measurements were calculated and compared with those inferred from experiment. We calculate an average tilt angle close to the SFG observed value of 35, an average surface density of free OH bonds close to the experimental value of about 2.8 × 10(18) m(-2), computed ratios of A(eff)'s that are very similar to those from the SFG experiment, and their absolute values that are in reasonable agreement with experiment. A one-parameter model was used to calculate these properties. The method utilizes results available from independent IR and Raman experiments to obtain some of the needed quantities, rather than calculating them ab initio. The present results provide microscopic information on water structure useful to applications such as in our recent theory of on-water heterogeneous catalysis.