Liu Jian
Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
J Chem Phys. 2014 Jun 14;140(22):224107. doi: 10.1063/1.4881518.
We show a new imaginary time path integral based method--path integral Liouville dynamics (PILD), which can be derived from the equilibrium Liouville dynamics [J. Liu and W. H. Miller, J. Chem. Phys. 134, 104101 (2011)] in the Wigner phase space. Numerical tests of PILD with the simple (white noise) Langevin thermostat have been made for two strongly anharmonic model problems. Since implementation of PILD does not request any specific form of the potential energy surface, the results suggest that PILD offers a potentially useful approach for general condensed phase molecular systems to have the two important properties: conserves the quantum canonical distribution and recovers exact thermal correlation functions (of even nonlinear operators, i.e., nonlinear functions of position or momentum operators) in the classical, high temperature, and harmonic limits.
我们展示了一种基于新的虚时路径积分的方法——路径积分刘维尔动力学（PILD），它可以从维格纳相空间中的平衡刘维尔动力学[J. Liu和W. H. Miller，《化学物理杂志》134, 104101 (2011)]推导得出。针对两个强非谐模型问题，已经使用简单（白噪声）朗之万恒温器对PILD进行了数值测试。由于PILD的实现不要求势能面具有任何特定形式，结果表明PILD为一般凝聚相分子系统提供了一种潜在有用的方法，使其具有两个重要特性：在经典、高温和谐波极限下保持量子正则分布并恢复精确的热关联函数（甚至是关于非线性算符的，即位置或动量算符的非线性函数）。
