Wang Haobin, Skinner David E, Thoss Michael
Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, NM 88003, USA.
J Chem Phys. 2006 Nov 7;125(17):174502. doi: 10.1063/1.2363195.
A numerically exact quantum mechanical approach is proposed to evaluate thermal rate constants for systems in a model condensed phase environment. Employing the reactive flux correlation function formalism, the approach efficiently combines the multilayer multiconfiguration time-dependent Hartree theory with an importance sampling scheme for thermal distribution of the initial states. The performance of the method is illustrated by applications to two models of condensed phase dynamics: the donor-acceptor electron transfer model also known as the spin-boson model and a model for proton transfer reactions in the condensed phase.
提出了一种数值精确的量子力学方法来评估模型凝聚相环境中系统的热速率常数。该方法采用反应通量相关函数形式，有效地将多层多组态含时 Hartree 理论与初始态热分布的重要性抽样方案相结合。通过应用于凝聚相动力学的两个模型来说明该方法的性能：供体 - 受体电子转移模型（也称为自旋 - 玻色子模型）和凝聚相中质子转移反应的模型。
