Coherence penalty functional: A simple method for adding decoherence in Ehrenfest dynamics
Coherence penalty functional: A simple method for adding decoherence in Ehrenfest dynamics
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DOI：
10.1063/1.4875702
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发表时间：
2014-05-21
影响因子：
4.4
通讯作者：
Prezhdo, Oleg V.
中科院分区：
文献类型：
--
作者：
Akimov, Alexey V.;Long, Run;Prezhdo, Oleg V.
提出了一种新的描述电子非绝热分子动力学退相干的半经典方法。该方法是制定的Escherifest动力学和Meyer-Miller-Thoss-Stock映射的时间依赖薛定谔方程到一个完全经典的哈密顿表示的理由。我们引入了一个相干惩罚功能（CPF），占退相干效应随机化的波函数相位和惩罚发展的相干性强的非绝热耦合区域。该方法的性能与几个模型和现实的系统证明。与其他半经典方法相比，CPF方法消除了人为干扰，提高了与模型的全量子计算的一致性。当应用于研究纳米系统中的电子转移动力学时，该方法显示出更高的预测时间尺度的准确性。CPF方法的简单性和高计算效率使其成为现实系统中应用的理想候选者。(C)2014 AIP Publishing LLC.
We present a new semiclassical approach for description of decoherence in electronically nonadiabatic molecular dynamics. The method is formulated on the grounds of the Ehrenfest dynamics and the Meyer-Miller-Thoss-Stock mapping of the time-dependent Schrodinger equation onto a fully classical Hamiltonian representation. We introduce a coherence penalty functional (CPF) that accounts for decoherence effects by randomizing the wavefunction phase and penalizing development of coherences in regions of strong non-adiabatic coupling. The performance of the method is demonstrated with several model and realistic systems. Compared to other semiclassical methods tested, the CPF method eliminates artificial interference and improves agreement with the fully quantum calculations on the models. When applied to study electron transfer dynamics in the nanoscale systems, the method shows an improved accuracy of the predicted time scales. The simplicity and high computational efficiency of the CPF approach make it a perfect practical candidate for applications in realistic systems. (C) 2014 AIP Publishing LLC.