Non-adiabatic Matsubara dynamics and non-adiabatic ring-polymer molecular dynamics
Non-adiabatic Matsubara dynamics and non-adiabatic ring-polymer molecular dynamics
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DOI：
10.1063/5.0042136
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发表时间：
2021-03-28
影响因子：
4.4
通讯作者：
Huo, Pengfei
中科院分区：
文献类型：
--
作者：
Chowdhury, Sutirtha N.;Huo, Pengfei
我们提出了非绝热松原动力学，计算电子非绝热系统的时间相关函数（TCF）的一般框架。这种新的形式主义是基于广义Kubo变换的TCF使用Wigner表示的核自由度和电子映射变量。通过在量子Liouvillian中去掉非松原核的简正模，并将这些简正模从TCF的表达式中显式积分出来，我们得到了非绝热松原动力学方法。在此基础上，进一步去掉了Matsubara Liouvillian的虚部，使核动量积分为真实的，得到了非绝热环聚合物分子动力学（NRPMD）方法。我们进一步证明了NRPMD模拟非平衡TCF的能力。这项工作提供了严格的理论基础，最近提出的几个状态相关的RPMD方法，并提供了一个通用的框架，在未来开发新的非绝热量子动力学方法。
We present the non-adiabatic Matsubara dynamics, a general framework for computing the time-correlation function (TCF) of electronically non-adiabatic systems. This new formalism is derived based on the generalized Kubo-transformed TCF using the Wigner representation for both the nuclear degrees of freedom and the electronic mapping variables. By dropping the non-Matsubara nuclear normal modes in the quantum Liouvillian and explicitly integrating these modes out from the expression of the TCF, we derived the non-adiabatic Matsubara dynamics approach. Further making the approximation to drop the imaginary part of the Matsubara Liouvillian and enforce the nuclear momentum integral to be real, we arrived at the non-adiabatic ring-polymer molecular dynamics (NRPMD) approach. We have further justified the capability of NRPMD for simulating the non-equilibrium TCF. This work provides the rigorous theoretical foundation for several recently proposed state-dependent RPMD approaches and offers a general framework for developing new non-adiabatic quantum dynamics methods in the future.