Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun, Beijing 100190, China.
J Phys Chem A. 2013 Jul 25;117(29):6196-204. doi: 10.1021/jp400462f. Epub 2013 Apr 18.
We investigate the applicability of the Ehrenfest and surface hopping methods to calculate electron transfer rates using the spin-boson model with different parameters. Rate constants are obtained from short time dynamics performed in both the diabatic and adiabatic basis sets. Numerical results and theoretical analysis show that these two methods can be reasonably accurate in the nonadiabatic limit, by staying close to an approximate Fermi's golden rule. Beyond the nonadiabatic limit, the calculated mixed quantum classical rates are compared with numerical exact results, and similar accuracy was found as in the nonadiabatic limit. The relation between the current finding and recent studies using the surface hopping method based on long time dynamics is also discussed. It is found that the short time dynamics could be more accurate in calculating rate constants using the mixed quantum classical methods.
我们研究了 Ehrenfest 和表面跳跃方法在使用不同参数的自旋-玻色子模型计算电子转移速率时的适用性。速率常数是从在绝热和非绝热基组中进行的短时间动力学中获得的。数值结果和理论分析表明，这两种方法在非绝热极限下通过接近近似的费米黄金定则，可以相当准确。在非绝热极限之外，计算出的混合量子经典速率与数值精确结果进行了比较，发现与非绝热极限一样具有相似的准确性。还讨论了当前研究与最近使用基于长时间动力学的表面跳跃方法的研究之间的关系。结果发现，在使用混合量子经典方法计算速率常数时，短时间动力学可能更准确。
