Extended hydrodynamic approach to quantum-classical nonequilibrium evolution. II. Application to nonpolar solvation

Abstract

The mixed quantum-classical formulation derived in our companion paper [D. Bousquet, K. H. Hughes, D. Micha, and I. Burghardt, J. Chem. Phys. 134, 064116 (2011)], which is based upon a hydrodynamic representation of the classical sector, is applied to nonequilibrium nonpolar solvation dynamics as exemplified by the solvation of the electronically excited NO molecule in a rare gas environment. Derived from a partition of the Hamiltonian into a primary (quantum) part and a secondary (classical) part the hydrodynamic equations are formulated for multi-quantum states and result in explicit equations of motion for populations and coherences. The hierarchy of hydrodynamic equations is truncated by the following approximate closure schemes: Gauss-Hermite closure, dynamical density functional theory approximation, and a generalized Maxwellian closure. A comparison of the dynamics using these three closure methods showed that the suitability of a particular closure scheme was dependent on the initial conditions and the nonequilibrium character of the dynamics.