School of Chemistry, Bangor University Bangor, Gwynedd LL57 2UW, United Kingdom.
J Chem Phys. 2012 Jan 7;136(1):014102. doi: 10.1063/1.3671378.
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.
我们在[D. Bousquet、K. H. Hughes、D. Micha 和 I. Burghardt，J. Chem. Phys. 134，064116 (2011)]的合作者论文中提出的混合量子经典公式，它基于经典部分的流体力学表示，被应用于非平衡非极性溶剂化动力学，例如电子激发的 NO 分子在稀有气体环境中的溶剂化。从哈密顿量的分区为主要（量子）部分和次要（经典）部分，流体力学方程是针对多量子态制定的，并导致了对群体和相干的明确运动方程。流体力学方程的层次被以下近似闭合方案截断：Gauss-Hermite 闭合、动力学密度泛函理论近似和广义麦克斯韦闭合。使用这三种闭合方法对动力学进行的比较表明，特定闭合方案的适用性取决于初始条件和动力学的非平衡性质。
