Department of Chemistry, Imperial College London UK.
Department of Chemistry and Biochemistry, University of Colorado, Boulder Boulder, CO, USA ; Département de Chimie, École Normale Supérieur, UMR ENS-CNRS-UPMC 8640 Paris, France.
Front Chem. 2014 Nov 21;2:97. doi: 10.3389/fchem.2014.00097. eCollection 2014.
Conical intersections play a major role in the current understanding of electronic de-excitation in polyatomic molecules, and thus in the description of photochemistry and photophysics of molecular systems. This article reviews aspects of the basic theory underlying the description of non-adiabatic transitions at conical intersections, with particular emphasis on the important case when the dynamics of the nuclei are treated classically. Within this classical nuclear motion framework, the main aspects of the surface hopping methodology in the conical intersection context are presented. The emerging picture from this treatment is that of electronic transitions around conical intersections dominated by the interplay of the nuclear velocity and the derivative non-adiabatic coupling vector field.
锥型交点在当前对多原子分子中电子退激发的理解中起着重要作用，因此也在分子体系的光化学和光物理描述中起着重要作用。本文回顾了描述锥型交点处非绝热跃迁的基础理论的各个方面，特别强调了当核动力学以经典方式处理时的重要情况。在这个经典核运动框架内，本文介绍了锥型交点环境中表面跳跃方法的主要方面。这种处理方法所呈现的图像是，锥型交点周围的电子跃迁主要由核速度和导数非绝热耦合矢量场的相互作用所支配。
