Shakib Farnaz A, Huo Pengfei
Department of Chemistry, University of Rochester , 120 Trustee Road, Rochester, New York 14627, United States.
J Phys Chem Lett. 2017 Jul 6;8(13):3073-3080. doi: 10.1021/acs.jpclett.7b01343. Epub 2017 Jun 22.
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.
我们应用最近提出的环聚合物表面跳跃（RPSH）方法来研究具有明确核量子效应的实时非绝热动力学。非绝热电子跃迁通过塔利的最少开关表面跳跃算法来描述，并且原子核的运动在扩展相空间中通过环聚合物哈密顿量进行量子化。将RPSH方法应用于模拟塔利的避免交叉模型，我们证明了核隧穿效应和零点能对于准确描述低初始动量下的透射和反射概率的关键作用。此外，在塔利的扩展耦合模型中，我们表明环聚合物量子化有效地捕捉了退相干，产生了更准确的反射概率。这些有前景的结果证明了使用RPSH作为一种准确且高效的方法将核量子效应纳入非绝热动力学模拟的潜力。
