Causo Maria Serena, Ciccotti Giovanni, Montemayor Daniel, Bonella Sara, Coker David F
Dipartimento di Fisica, Università "La Sapienza", Piazzale Aldo Moro, 2, 00185 Roma, Italy.
J Phys Chem B. 2005 Apr 14;109(14):6855-65. doi: 10.1021/jp045208b.
We generalize the linearized path integral approach to evaluate quantum time correlation functions for systems best described by a set of nuclear and electronic degrees of freedom, restricting ourselves to the adiabatic approximation. If the operators in the correlation function are nondiagonal in the electronic states, then this adiabatic linearized path integral approximation for the thermal averaged quantum dynamics presents interesting and distinctive features, which we derive and explore in this paper. The capability of these approximations to accurately reproduce the behavior of physical systems is demonstrated by calculating the diffusion constant for an excess electron in a metal-molten salt solution.
我们推广线性化路径积分方法，以评估由一组核自由度和电子自由度最佳描述的系统的量子时间关联函数，这里我们限于绝热近似。如果关联函数中的算符在电子态上是非对角的，那么这种用于热平均量子动力学的绝热线性化路径积分近似呈现出有趣且独特的特征，我们将在本文中推导并探讨这些特征。通过计算金属 - 熔盐溶液中过量电子的扩散常数，证明了这些近似准确再现物理系统行为的能力。
