Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario M1C 1A4, Canada.
J Chem Phys. 2017 Aug 14;147(6):064106. doi: 10.1063/1.4985925.
We investigate geometric phase (GP) effects in nonadiabatic transitions through a conical intersection (CI) in an N-dimensional linear vibronic coupling (ND-LVC) model. This model allows for the coordinate transformation encompassing all nonadiabatic effects within a two-dimensional (2D) subsystem, while the other N - 2 dimensions form a system of uncoupled harmonic oscillators identical for both electronic states and coupled bi-linearly with the subsystem coordinates. The 2D subsystem governs ultra-fast nonadiabatic dynamics through the CI and provides a convenient model for studying GP effects. Parameters of the original ND-LVC model define the Hamiltonian of the transformed 2D subsystem and thus influence GP effects directly. Our analysis reveals what values of ND-LVC parameters can introduce symmetry breaking in the 2D subsystem that diminishes GP effects.
我们通过 N 维线性振子耦合（ND-LVC）模型中的锥形交叉（CI）研究非绝热跃迁中的几何相位（GP）效应。该模型允许在二维（2D）子系统中包含所有非绝热效应的坐标变换，而其他 N-2 个维度形成了一个对于两个电子态相同的、与子系统坐标双线性耦合的非耦合谐振子系统。2D 子系统通过 CI 控制超快非绝热动力学，并提供了一个研究 GP 效应的便利模型。原始 ND-LVC 模型的参数定义了变换后的 2D 子系统的哈密顿量，因此直接影响 GP 效应。我们的分析揭示了哪些 ND-LVC 参数值可以在 2D 子系统中引入对称性破缺，从而减弱 GP 效应。
