Coupled-channels quantum theory of electronic flux density in electronically adiabatic processes: fundamentals.
Coupled-channels quantum theory of electronic flux density in electronically adiabatic processes: fundamentals.
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电子绝热过程中电子通量密度的耦合通道量子理论：基础知识。
DOI：
10.1021/jp207843z
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
D. J. Diestler
中科院分区：
文献类型：
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作者：
D. J. Diestler
Born-Oppenheimer （BO）对电子绝热分子过程的描述预测电子通量密度（j(e)）会消失，=1/2∫dR[Δ(b) (x；R) - Δ(a) (x；R)]，尽管电子肯定会随着原子核的运动而运动。本文是两篇文章中的第一篇，提出了一种量子力学“耦合通道”（CC）理论，该理论允许从电子绝热BO波函数中近似提取j(e)。CC理论详细描述了H(2)(+)，在这种情况下，j(e)可以分解成与两个通道α (=a,b)相关的组件，每个通道对应于“内部”原子α（质子a或b加电子）与另一个原子核β（质子b或a）的“碰撞”。电子的动态作用，它可以瞬间适应原子核的运动，被淹没在与每个通道（α）相关的有效电子概率（种群）密度Δ（α）中。Δ（α）密度由（时间无关的）BO电子能量特征函数决定，该特征函数参数依赖于原子核的构型，其运动由通常的BO核Schrödinger方程控制。推导了H(2)（+）的电子通量密度的直观的形式表达式。
The Born-Oppenheimer (BO) description of electronically adiabatic molecular processes predicts a vanishing electronic flux density (j(e)), =1/2∫dR[Δ(b) (x;R) - Δ(a) (x;R)] even though the electrons certainly move in response to the movement of the nuclei. This article, the first of a pair, proposes a quantum-mechanical "coupled-channels" (CC) theory that allows the approximate extraction of j(e) from the electronically adiabatic BO wave function . The CC theory is detailed for H(2)(+), in which case j(e) can be resolved into components associated with two channels α (=a,b), each of which corresponds to the "collision" of an "internal" atom α (proton a or b plus electron) with the other nucleus β (proton b or a). The dynamical role of the electron, which accommodates itself instantaneously to the motion of the nuclei, is submerged in effective electronic probability (population) densities, Δ(α), associated with each channel (α). The Δ(α) densities are determined by the (time-independent) BO electronic energy eigenfunction, which depends parametrically on the configuration of the nuclei, the motion of which is governed by the usual BO nuclear Schrödinger equation. Intuitively appealing formal expressions for the electronic flux density are derived for H(2)(+).