Collision induced transitions between 2Π and 2Σ states of diatomic molecules: Quantum theory and collisional propensity rules
Collision induced transitions between 2Π and 2Σ states of diatomic molecules: Quantum theory and collisional propensity rules
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双原子分子 2π 和 2Σ 态之间碰撞引起的转变：量子理论和碰撞倾向规则
DOI：
10.1063/1.450831
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发表时间：
1986
影响因子：
4.4
通讯作者：
G. C. Corey
中科院分区：
文献类型：
--
作者：
M. Alexander;G. C. Corey
我们发展了精确的量子描述，没有任何动力学近似，旋转非弹性碰撞诱导的双原子分子的2Π和2 π电子态之间的过渡。一个明确的连接之间的矩阵元素的静电耦合，描述在一个渐近精确的非绝热的基础上，和从头计算的结果适当的原子-分子绝热电子波函数的A'和A'对称性。对量子紧耦合方程的分析表明，在E → E能量转移的描述中使用弗兰克-康登近似是不合理的，而且，在涉及同素双原子分子的碰撞中，分子波函数的s/a置换-反转对称性将严格守恒。无限阶突近似扩展到电子非弹性2Π → 2 π过程，使我们能够预测两个新的碰撞倾向规则：（a）当Δ J=0时，截面将...
We develop the exact quantum description, free of any dynamical approximations, of rotationally inelastic collision induced transitions between 2Π and 2Σ electronic states of a diatomic molecule. An explicit connection is made between the matrix elements of the electrostatic coupling, described in an asymptotically exact diabatic basis, and the results of an ab initio calculation of the appropriate atom–molecule adiabatic electronic wave functions of A’ and A‘ symmetry. Analysis of the quantum close‐coupled equations demonstrates that the use of Franck–Condon approximations in the description of E → E energy transfer is unjustified and, furthermore, that in collisions involving homonuclear diatomic molecules the s/a permutation‐inversion symmetry of the molecular wave functions will be rigorously conserved. The extension of the infinite‐order sudden approximation to electronically inelastic 2Π → 2Σ processes allows us to predict two new collisional propensity rules: (a) When Δ J=0 the cross sections will ...