Nuclear quantum effects in electronic (non)adiabatic dynamics
Nuclear quantum effects in electronic (non)adiabatic dynamics
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DOI：
10.1140/epjb/e2018-90144-3
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发表时间：
2018-07-02
影响因子：
1.6
通讯作者：
Ciccotti, Giovanni
中科院分区：
文献类型：
--
作者：
Agostini, Federica;Tavernelli, Ivano;Ciccotti, Giovanni
基于轨迹的激发态非绝热动力学方法是描述复杂分子系统对光激发的响应的有前景的模拟技术。它们提供了电子和原子核耦合量子动力学的近似描述，试图访问日益复杂的系统。这些近似设计的核心问题是正确考虑电子-核耦合和问题的量子特征。在本文中，我们在电子-核波函数精确分解的框架中解决该问题，重新推导和改进了最近开发的用于求解精确分解方程的耦合轨迹混合量子经典（CT-MQC）算法。特别是，推导了在 CT-MQC 中包含量子核效应的程序，并在不同状态下的模型系统上进行了测试。
Trajectory-based approaches to excited-state, nonadiabatic dynamics are promising simulation techniques to describe the response of complex molecular systems upon photo-excitation. They provide an approximate description of the coupled quantum dynamics of electrons and nuclei trying to access systems of growing complexity. The central question in the design of those approximations is a proper accounting of the coupling electron-nuclei and of the quantum features of the problem. In this paper, we approach the problem in the framework of the exact factorization of the electron-nuclear wavefunction, re-deriving and improving the coupled-trajectory mixed quantum-classical (CT-MQC) algorithm recently developed to solve the exact-factorization equations. In particular, a procedure to include quantum nuclear effects in CT-MQC is derived, and tested on a model system in different regimes.