Curchod Basile F E, Rauer Clemens, Marquetand Philipp, González Leticia, Martínez Todd J
Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
Institute of Theoretical Chemistry, University of Vienna, Währinger Straße 17, 1090 Vienna, Austria.
J Chem Phys. 2016 Mar 14;144(10):101102. doi: 10.1063/1.4943571.
Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.
完全多重产卵法是一种形式上精确的方法，用于描述超越玻恩-奥本海默近似的分子体系激发态动力学。然而，到目前为止，它仅限于描述具有相同自旋多重性的电子态之间发生的无辐射跃迁。本通讯基于自旋绝热表示，将完全从头算多重产卵法推广到内转换（由非绝热耦合项介导）和系间窜越事件（由自旋-轨道耦合矩阵元触发）。两个数值应用的结果，一个模型体系和硫代甲醛的失活，验证了所提出的形式体系及其实现。
