The dynamical properties of liquid water play an important role in many processes in nature, including solvation processes in bulk and at interfaces.  The first part of the talk is focused on the infrared (IR) absorption spectrum of liquid water based on the linearized semiclassical initial value representation (LSC-IVR) with the local Gaussian approximation (LGA) [J. Liu and W. H. Miller, J. Chem. Phys. 131  , 074113 (2009)] and an ab initio based, flexible, polarizable Thole-type model (TTM3-F) [G. S. Fanourgakis and S. S. Xantheas, J. Chem. Phys. 128  , 074506 (2008)]. Although the LSC-IVR (LGA) gives the exact result for the isolated three-dimensional shifted harmonic stretching model, it yields a blueshifted peak position for the more realistic anharmonic stretching potential. By using the short-time information of the LSC-IVR correlation function; however, it is shown how one can obtain more accurate results for the position of the stretching peak.  The present results offer valuable insight into future attempts to improve the accuracy of the TTM3-F potential or other ab initio-based models in describing liquid water.The second part of the talk will describe how solvent molecules affect/change the photodynamics of the chromorphore based on our recent investigation with the full multiple spawning (FMS) method [T. J. Martinez, Acc. Chem. Res. 39, 119 (2006)] and phase space dynamics.

Insights in quantum dynamical effects in liquid water from a semiclassical study with an ab initio-based flexible and polarizable force field

244th National Meeting (2012)

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