Zhao Yi, Li Xiang, Zheng Zilong, Liang Wanzhen
Hefei National Laboratory for Physical Sciences at Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, People's Republic of China.
J Chem Phys. 2006 Mar 21;124(11):114508. doi: 10.1063/1.2178323.
The nonadiabatic transition state theory proposed recently by Zhao et al. [J. Chem. Phys. 121, 8854 (2004)] is extended to calculate rate constants of complex systems by using the Monte Carlo and umbrella sampling methods. Surface hopping molecular dynamics technique is incorporated to take into account the dynamic recrossing effect. A nontrivial benchmark model of the nonadiabatic reaction in the condensed phase is used for the numerical test. It is found that our semiclassical results agree well with those produced by the rigorous quantum mechanical method. Comparing with available analytical approaches, we find that the simple statistical theory proposed by Straub and Berne [J. Chem. Phys. 87, 6111 (1987)] is applicable for a wide friction region although their formula is obtained using Landau-Zener [Phys. Z. Sowjetunion 2, 46 (1932); Proc. R. Soc. London, Ser. A 137, 696 (1932)] nonadiabatic transition probability along a one-dimensional diffusive coordinate. We also investigate how the nuclear tunneling events affect the dependence of the rate constant on the friction.
赵等人[《化学物理杂志》121, 8854 (2004)]最近提出的非绝热过渡态理论通过使用蒙特卡罗方法和伞形抽样方法进行扩展，以计算复杂体系的速率常数。引入表面跳跃分子动力学技术来考虑动态再穿越效应。凝聚相中一个非平凡的非绝热反应基准模型用于数值测试。结果发现，我们的半经典结果与严格量子力学方法得到的结果吻合得很好。与现有的解析方法相比，我们发现斯特劳布和伯恩[《化学物理杂志》87, 6111 (1987)]提出的简单统计理论适用于较宽的摩擦区域，尽管他们的公式是利用朗道 - 齐纳[《苏联物理杂志》2, 46 (1932); 《伦敦皇家学会学报》A辑137, 696 (1932)]沿一维扩散坐标的非绝热跃迁概率得到的。我们还研究了核隧穿事件如何影响速率常数对摩擦的依赖性。
