In light of the rapid progress of ultrafast chemical dynamics driven by the pulse lasers having width as short as several tens of attoseconds, we herein develop a theory of nonadiabatic electron wavepacket dynamics in condensed phases, with which to directly track the dynamics of electronic-state mixing such as electron transfer in liquid solvents. Toward this goal, we combine a theory of path-branching representation for nonadiabatic electron wavepacket dynamics in vacuum {a mixed quantum-classical representation, Yonehara and Takatsuka [J. Chem. Phys. 129, 134109 (2008)]} and a theory of entropy functional to treat chemical dynamics in condensed phases {a mixed dynamical-statistical representation, Takatsuka and Matsumoto [Phys. Chem. Chem. Phys. 18, 1771 (2016)]}. Difficulty and complexity in the present theoretical procedure arise in embedding the Schrödinger equation into classically treated statistical environment. Nevertheless, the resultant equations of motion for electronic-state mixing due to the intrinsic nonadiabatic interactions and solute-solvent interactions, along with the force matrix that drives nuclear branching paths, both turn out to be clear enough to make it possible to comprehend the physical meanings behind. We also discuss briefly the nonvalidness of naive application of the notion of nonadiabatic transition dynamics among free energy surfaces.

中文翻译：

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凝聚相中的分子非绝热电子动力学理论

鉴于宽度短至几十个阿秒的脉冲激光器驱动的超快化学动力学的快速发展，我们在本文中提出了凝聚态的非绝热电子波包动力学的理论，通过该理论可直接跟踪电子态的动力学混合，例如在液体溶剂中进行电子转移。为了实现这一目标，我们结合了在真空中非绝热电子波包动力学的路径分支表示理论（一种混合的量子经典表示形式，Yonehara和Takatsuka [J. 化学 物理 129，134109（2008）]}和熵功能的理论来治疗在冷凝阶段{的混合动力-统计表示，高冢和松本[物理学化学动力学。化学 化学 物理 18岁，1771（2016）]}。将理论上的Schrödinger方程嵌入经典处理的统计环境中会产生困难和复杂性。然而，由于固有的非绝热相互作用和溶质-溶剂相互作用而产生的电子态混合运动方程，以及驱动核分支路径的力矩阵，都变得足够清晰，可以理解物理性质。背后的含义。我们还简要讨论了自由能表面之间非绝热转变动力学概念的幼稚应用的无效性。