Ring Polymer Surface Hopping: Incorporating Nuclear Quantum Effects into Nonadiabatic Molecular Dynamics Simulations.
Ring Polymer Surface Hopping: Incorporating Nuclear Quantum Effects into Nonadiabatic Molecular Dynamics Simulations.
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DOI：
10.1021/acs.jpclett.7b01343
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发表时间：
2017-06
期刊：
影响因子：
--
通讯作者：
F. Shakib;P. Huo
中科院分区：
文献类型：
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作者：
F. Shakib;P. Huo
我们应用最近提出的环聚合物表面跳跃(RPSH)方法研究了具有显式核量子效应的实时非绝热动力学。非绝热电子跃迁通过Tully的最少开关表面跳跃算法描述，原子核的运动通过环聚合物哈密顿量在扩展的相空间中被量子化。用RPSH方法模拟了Tully避开交叉模型，论证了核隧穿效应和零点能量对于准确描述低初始动量下的透射率和反射率的关键作用。此外，在Tully的扩展耦合模型中，我们证明了环聚合物量子化有效地捕获了退相干，产生了更准确的反射几率。这些有希望的结果表明，利用RPSH作为一种准确而有效的方法将核量子效应纳入非绝热动力学模拟是有潜力的。
We apply a recently proposed ring polymer surface hopping (RPSH) approach to investigate the real-time nonadiabatic dynamics with explicit nuclear quantum effects. The nonadibatic electronic transitions are described through Tully's fewest-switches surface hopping algorithm and the motion of the nuclei are quantized through the ring polymer Hamiltonian in the extended phase space. Applying the RPSH method to simulate Tully's avoided crossing models, we demonstrate the critical role of the nuclear tunneling effect and zero-point energy for accurately describing the transmission and reflection probabilities with low initial momenta. In addition, in Tully's extended coupling model, we show that the ring polymer quantization effectively captures decoherence, yielding more accurate reflection probabilities. These promising results demonstrate the potential of using RPSH as an accurate and efficient method to incorporate nuclear quantum effects into nonadiabatic dynamics simulations.