Surface Hopping Dynamics beyond Nonadiabatic Couplings for Quantum Coherence
Surface Hopping Dynamics beyond Nonadiabatic Couplings for Quantum Coherence
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DOI：
10.1021/acs.jpclett.8b00060
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发表时间：
2018-03-01
影响因子：
5.7
通讯作者：
Min, Seung Kyu
中科院分区：
文献类型：
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作者：
Ha, Jong-Kwon;Lee, In Seong;Min, Seung Kyu
在非绝热动力学建模中，正确描述电子-核耦合是至关重要的。在传统的半经典或混合量子-经典动力学中，量子电子态与经典核轨迹之间的耦合是由与经典核动量耦合的非绝热耦合向量控制的。这使我们能够开发一种非常强大的非绝热动力学算法，即表面跳跃动力学，它可以描述核波包的分裂和详细的平衡。尽管它的效率和实用性，但由于对电子-核耦合的错误解释，它缺乏量子退相干性。本文提出了一种基于分子波函数精确分解的精确电子-核相关的表面跳跃算法。该算法的计算成本与现有的表面跳变方法相当。双态模型和多维多态现实分子的数值模拟表明，非绝热耦合项以外的电子-核耦合可以很好地描述量子相干性。
Description of correct electron-nuclear couplings is crucial in modeling of nonadiabatic dynamics. Within traditional semiclassical or mixed quantum- classical dynamics, the coupling between quantum electronic states and classical nuclear trajectories is governed by nonadiabatic coupling vectors coupled to classical nuclear momenta. This enables us to develop a very powerful nonadiabatic dynamics algorithm, namely, surface hopping dynamics, which can describe the splitting of nuclear wave packets and detailed balance. Despite its efficiency and practicality, it suffers from the lack of quantum decoherence due to incorrect accounts for the electron- nuclear coupling. Here we present a new surface hopping algorithm based on the exact electron-nuclear correlation from the exact factorization of molecular wave functions. This algorithm demands comparable computational costs to existing surface hopping methods. Numerical simulations with two-state models and a multidimensional multistate realistic molecule show that the electron-nuclear coupling beyond the nonadiabatic coupling terms can describe the quantum coherence properly.