混合量子-经典方法计算电荷转移速率及其在实际体系中的应用(英文)  

Mixed Quantum-Classical Approaches to Calculating Charge Transfer Rate Constants:Applications to Realistic Systems

作　　者：南广军[1,2] 郑仁慧[1] 史强[1] 帅志刚[3,4] 

机构地区：[1]中国科学院化学研究所、分子动态与稳态结构国家审点实验室、北京分子科学国家实验室,北京100190 [2]哈尔滨工业大学基础与交叉科学研究院理论与模拟化学研究所,哈尔滨150080 [3]中国科学院化学研究所、有机固体院蕈点实验室、北京分子科学国家实验室,北京100190 [4]清华大学化学系,北京100084

出　　处：《物理化学学报》2010年第7期1755-1760,共6页Acta Physico-Chimica Sinica

基　　金：supported by the National Natural Science Foundation of China(20733006,20873157,20833004,20903101);Funds of the Chinese Academy of Sciences(KJCX2.YW.H17 and the Hundred Talents Project);Fundamental Research Funds for the Central Universities,China(HIT.NSRIF.2009084)~~

摘　　要：混合量子-经典方法在复杂分子体系动力学过程的模拟方面有重要应用.我们采用Ehrenfest方法、surfacehopping方法和混合量子经典Liouville方程计算了在非绝热极限下的电荷转移速率.然后将这三种方法应用于有机半导体材料电荷转移速率的计算.研究结果发现,Ehrenfest方法和surface hopping方法可能严重偏离正确的结果.偏离的原因是这两种方法没有正确处理相干项的运动,而且这种偏离在涉及到高频模式时显得更加严重.Mixed quantum-classical methods are of great interest in simulating dynamic processes of complex molecular systems.We investigated the application of the Ehrenfest method, the surface hopping method, and the mixed quantum classical Liouville equation method to calculate charge transfer rates in the nonadiabatic limit.The three methods were applied to realistic problems of charge transfer in organic semiconductor materials.We found that both the Ehrenfest and surface hopping methods may deviate significantly from the correct result.This deviation is due to an incorrect treatment of the coherence term, and is more severe when high frequency modes are involved.

关 键 词：混合量子-经典方法 电荷转移 有机半导体材料 

分 类 号：O649[理学—物理化学]