Adiabatic molecular properties beyond the Born–Oppenheimer approximation. Complete adiabatic wave functions and vibrationally induced electronic current density
Adiabatic molecular properties beyond the Born–Oppenheimer approximation. Complete adiabatic wave functions and vibrationally induced electronic current density
复制标题
超越玻恩-奥本海默近似的绝热分子特性和振动感应电子电流密度。
DOI：
10.1063/1.445588
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发表时间：
1983
影响因子：
4.4
通讯作者：
L. Nafie
中科院分区：
文献类型：
--
作者：
L. Nafie
提出了超越Born-Oppenheimer（BO）近似描述绝热分子行为的概念和数学基础。传统的非绝热修正BO近似示出包含一个动能诱导绝热部分和一个完整的非绝热，或非绝热，部分。对新绝热项的最低阶贡献可以描述为动量绝热，并且与传统的BO位置绝热项互补。一个完整的绝热波函数包括涉及位置和动量的贡献，提供了一个完整的描述的电子概率密度的核运动的动态响应。该响应由分子的笛卡尔坐标空间中所有点的核动量诱导的电子电流密度和核位移诱导的电子电荷通量密度组成。这些核感应电荷通量和电流服从一个方程的连续性守恒的电子电荷。给出了红外吸收强度的位置和速度公式与电荷通量和电流之间的关系。
The conceptual and mathematical basis for describing adiabatic molecular behavior beyond the Born–Oppenheimer (BO) approximation is presented. The traditional nonadiabatic corrections to the BO approximation are shown to contain a kinetic energy induced adiabatic part and a complete nonadiabatic, or diabatic, part. The lowest order contributions to the new adiabatic terms can be described as momentum adiabatic and are complementary to the traditional BO position adiabatic terms. A complete adiabatic wave function comprised of contributions involving position and momentum is obtained that provides a complete description of the response of the electron probability density to the dynamics of the nuclear motion. This response is comprised of nuclear momentum induced electronic current density and nuclear displacement induced electronic charge flux density for all points in the Cartesian coordinate space of the molecule. These nuclear induced charge fluxes and currents are shown to obey an equation of continuity for the conservation of electronic charge. Relations between the position and velocity formulations of infrared absorption intensity and the charge fluxes and currents are provided.