Nonadiabatic representations of the 1Σ+u and 1Πu states of the N2 molecule
Nonadiabatic representations of the 1Σ+u and 1Πu states of the N2 molecule
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DOI：
10.1063/1.446166
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发表时间：
1983-09
影响因子：
4.4
通讯作者：
D. Stahel;M. Leoni;K. Dressler
中科院分区：
文献类型：
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作者：
D. Stahel;M. Leoni;K. Dressler
N2的偶极允许吸收光谱中与最低三个电子1 π +u和最低三个电子1Πu态相关的振动带在电子耦合非绝热态的基础上以及在核动量耦合绝热态的基础上表示。定义的非绝热态和它们的电子耦合能量的参数首先通过拟合的振动相互作用矩阵的本征值的观察。耦合振子方程直接用约翰逊的数值积分方法求解，非绝热表示通过矩阵方法和耦合方程迭代重新确定。在价态和里德伯型态（B′+c′+e′）1 +u和（B ′ +c+o）1 u的非绝热基中，用R独立的电子耦合能得到的实验振动项、B值和吸收强度的拟合令人满意。与相应的绝热表象比较表明，非绝热微扰的结果与绝热表象一致。
The vibronic bands in the dipole‐allowed absorption spectrum of N2 associated with the lowest three electronic 1Σ+u and the lowest three electronic 1Πu states are represented in a basis of electronically coupled diabatic states as well as in the basis of nuclear‐momentum coupled adiabatic states. Parameters defining the diabatic states and their electronic coupling energies are first evaluated by fitting the eigenvalues of a vibronic interaction matrix to the observations. The coupled‐oscillator equations are then solved directly by Johnson’s numerical integration method and the diabatic representation is redetermined via the matrix method and coupled equations iteratively. The fit of the experimental vibronic terms, B values, and absorption intensities achieved with R‐independent electronic coupling energies in a diabatic basis of valence and Rydberg‐type states (b′+c′+e′)1Σ+u and (b+c+o)1Πu is satisfactory. Comparison with the corresponding adiabatic representation shows that the nonadiabatic perturbati...