School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom.
J Chem Phys. 2010 Jun 28;132(24):244111. doi: 10.1063/1.3442747.
This article proposes an improved version of recently developed multiconfigurational Ehrenfest approach to quantum dynamics. The idea of the approach is to use frozen Gaussians (FG) guided by Ehrenfest trajectories as a basis set for fully quantum propagation. The method is applied to simulation of nonadiabatic dynamics of pyrazine and shows that nonadiabatic dynamics on two coupled electronic states S(2) and S(1), which determines pyrazine absorption spectrum, can be simulated with the help of a basis comprised of very small number of trajectory guided basis functions. For the 24 dimensional (24D) model, good results were obtained with the basis of only 250 trajectories guided FG per electronic state. The efficiency of the method makes it particularly suitable for future application together with direct dynamics, calculating potentials on the fly.
本文提出了一种改进的多组态 Ehrenfest 量子动力学方法。该方法的思想是使用 Ehrenfest 轨迹引导的冻结高斯（FG）作为完全量子传播的基函数集。该方法应用于吡嗪的非绝热动力学模拟，表明可以使用由非常少量轨迹引导基函数组成的基来模拟决定吡嗪吸收光谱的两个耦合电子态 S(2)和 S(1)上的非绝热动力学。对于 24 维（24D）模型，仅使用每个电子态 250 条轨迹引导 FG 的基即可获得良好的结果。该方法的效率使其特别适合与直接动力学一起应用，实时计算势能。
