Abstract

A two-electron model describing vibronic and spin-orbit couplings of ³Π and ³Σ⁺ electronic states in linear triatomic molecules is proposed. The analysis is based on the use of an ab initio Breit–Pauli form of the spin-orbit coupling operator. Electronic Hamiltonian symmetry operators are shown to involve both spatial operations (acting on electronic coordinates) and matrix operations (acting on electron spins). In our analysis, we take into account only deformation π-modes, and the resulting 9 × 9 vibronic matrix actually describes the relativistic Renner pseudo-effect (³Π + ³Σ⁺) × π. The eigenvalues of the vibronic matrix (i.e., potential energy surfaces) have an axial symmetry, however, they cannot be represented by analytical expressions. The calculated vibronic Hamiltonian contains six electrostatic and 16 spin-orbit real parameters.

中文翻译：

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线性三原子分子中3Π和3Σ+电子态的振动和自旋轨道耦合

摘要

描述的电子振动和自旋轨道耦合的两电子模型³ Π和^3个Σ ⁺线性三原子分子的电子态提出。该分析基于自旋轨道耦合算子的从头算Breit-Pauli形式的使用。电子哈密顿对称算子被证明涉及空间操作（作用于电子坐标）和矩阵操作（作用于电子自旋）。在我们的分析中，我们只考虑变形的π模式，并将所得9×9的电子振动矩阵实际上描述相对论伦纳伪效果（³ Π+ ³ Σ ⁺）×π。振动电子矩阵（即势能表面）的特征值具有轴向对称性，但是无法用解析表达式表示。计算的振动哈密顿量包含六个静电和16个自旋轨道实参。