Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario M1C 1A4, Canada.
J Chem Phys. 2013 Dec 21;139(23):234103. doi: 10.1063/1.4844095.
In molecular systems containing conical intersections (CIs), a nontrivial geometric phase (GP) appears in the nuclear and electronic wave functions in the adiabatic representation. We study GP effects in nuclear dynamics of an N-dimensional linear vibronic coupling (LVC) model. The main impact of GP on low-energy nuclear dynamics is reduction of population transfer between the local minima of the LVC lower energy surface. For the LVC model, we proposed an isometric coordinate transformation that confines non-adiabatic effects within a two-dimensional subsystem interacting with an N - 2 dimensional environment. Since environmental modes do not couple electronic states, all GP effects originate from nuclear dynamics within the subsystem. We explored when the GP affects nuclear dynamics of the isolated subsystem, and how the subsystem-environment interaction can interfere with GP effects. Comparing quantum dynamics with and without GP allowed us to devise simple rules to determine significance of the GP for nuclear dynamics in this model.
在含有锥形交叉（CI）的分子系统中，在绝热表示中，核和电子波函数中会出现非平庸的几何相位（GP）。我们研究了核动力学中 N 维线性振子耦合（LVC）模型的 GP 效应。GP 对低能核动力学的主要影响是减少 LVC 下能面局部极小值之间的种群转移。对于 LVC 模型，我们提出了一种等距坐标变换，将非绝热效应限制在与 N-2 维环境相互作用的二维子系统内。由于环境模式不耦合电子态，所有的 GP 效应都源于子系统内的核动力学。我们探讨了 GP 何时影响孤立子系统的核动力学，以及子系统-环境相互作用如何干扰 GP 效应。比较有无 GP 的量子动力学使我们能够设计出简单的规则，以确定该模型中 GP 对核动力学的重要性。
