title: 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.
authors.affiliation: School of Chemistry, Bangor University Bangor, Gwynedd LL57 2UW, United Kingdom. keith.hughes@bangor.ac.uk
authors.forename: Keith H
authors.initials: KH
authors.lastname: Hughes
authors.forename: Sean N
authors.initials: SN
authors.lastname: Baxter
authors.forename: David
authors.initials: D
authors.lastname: Bousquet
authors.forename: Padmanaban
authors.initials: P
authors.lastname: Ramanathan
authors.forename: Irene
authors.initials: I
authors.lastname: Burghardt
mesh_terms: D009569:Nitric Oxide / Q000737:chemistry; D011789:Quantum Theory; D012995:Solubility; D012997:Solvents / Q000737:chemistry*
chemical_list: D012997:Solvents; D009569:Nitric Oxide