物理化学学报 >> 2010, Vol. 26 >> Issue (07): 1755-1760.doi: 10.3866/PKU.WHXB20100735

化学动力学和分子动态学 上一篇    下一篇

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

南广军, 郑仁慧, 史强, 帅志刚   

  1. 中国科学院化学研究所,分子动态与稳态结构国家重点实验室, 北京分子科学国家实验室, 北京 100190
    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
    中国科学院化学研究所, 有机固体院重点实验室, 北京分子科学国家实验室, 北京 100190
    清华大学化学系, 北京 100084
  • 收稿日期:2010-03-24 修回日期:2010-05-21 发布日期:2010-07-02
  • 通讯作者: 史强, 帅志刚 E-mail:qshi@iccas.ac.cn; zgshuai@iccas.ac.cn

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

NAN Guang-Jun, ZHENG Ren-Hui, SHI Qiang, SHUAI Zhi-Gang   

  1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
    Institute of Theoretical and Simulational Chemistry, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080, P. R. China
    Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
    Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
  • Received:2010-03-24 Revised:2010-05-21 Published:2010-07-02
  • Contact: SHI Qiang, SHUAI Zhi-Gang E-mail:qshi@iccas.ac.cn; zgshuai@iccas.ac.cn

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、surface hopping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.

关键词: 混合量子-经典方法, 电荷转移, 有机半导体材料

Abstract:

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.

Key words: Mixed quantum-classical method, Charge transfer, Organic semiconductor material

MSC2000: 

  • O649