Electron Transition Current Density in Molecules. 1. Non-Born−Oppenheimer Theory of Vibronic and Vibrational Transitions
Electron Transition Current Density in Molecules. 1. Non-Born−Oppenheimer Theory of Vibronic and Vibrational Transitions
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分子中的电子跃迁电流密度 1. 非玻恩-奥本海默振动跃迁理论。
DOI：
10.1021/jp9706137
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发表时间：
1997
影响因子：
2.9
通讯作者：
L. Nafie
中科院分区：
文献类型：
--
作者：
L. Nafie
定义了分子中两个定态之间振动跃迁的单粒子电子跃迁电流密度。TCD的表达式开发使用完全绝热（CA）的形式主义，其中的电子波函数进行明确的依赖于核动量，以及通常的依赖于核位置。在电子振动跃迁的情况下，主要的非玻恩-奥本海默（non-BO），核动量相关的贡献TCD伴随着一个不太重要的BO，核位置相关的贡献。对于单个电子状态内的振动跃迁，BO贡献消失，仅留下非BO、核动量驱动的TCD。在纯电子跃迁或单个电子态内的振动跃迁的极限下，证明了电子TCD满足任意一对定态的电子跃迁几率密度（TPD）守恒的连续性方程。TCD是一个向量场，具有...
The one-particle electron transition current density (TCD) for vibronic transitions between pairs of stationary states in molecules is defined. Expressions for TCD are developed using the complete adiabatic (CA) formalism in which the electronic wave function carries an explicit dependence on the nuclear momenta, as well as the usual dependence on nuclear positions. In the case of vibronic transitions, the principal non-Born−Oppenheimer (non-BO), nuclear-momentum-dependent contribution to TCD is accompanied by a less important BO, nuclear-position-dependent contribution. For vibrational transitions within a single electronic state, the BO contribution vanishes, leaving only non-BO, nuclear-momentum-driven TCD. In the limit of pure electronic transitions, or vibrational transitions within a single electronic state, it is shown that electron TCD satisfies the continuity equation for the conservation of electron transition probability density (TPD) for any pair of stationary states. TCD is a vector field hav...