Liu Yadong, Liu Yong, Liu Yahong, Zhang Cunhua, Li Rui, Yan Bing
Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012, China.
Department of Physics, College of Science, Qiqihar University, Qiqihar 161006, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2021 Feb 15;247:119147. doi: 10.1016/j.saa.2020.119147. Epub 2020 Nov 4.
In this paper, we have carried out high-level ab initio calculations on the electronic states of GeH with the configuration interaction method. The spin-orbit coupling (SOC), core-valence correlation (CV), scalar relativistic effects and Davidson correction (+Q) are included. The potential energy curves (PECs) of 13 Λ-S correlated with the four lowest dissociation limits and 32 Ω electronic states generated from those Λ-S states are obtained. Our results indicate that the first Σ and second Π states are adiabatically correlated with the dissociation limit Ge(P) + H(S), which is different from the previously reported Ge(P) + H(S). From the computed PECs, the spectroscopic constants of the Λ-S and Ω states are determined, which are in good agreement with previous experiments. The dipole moments (DMs) for Λ-S electronic states are also investigated. With the help of spin-orbit coupling matrix involving the 1Σ and 2Π states, the intricate couplings related with the crossing states are revealed, and the weak predissociation for ν' ≥0 vibrational levels of 1Σ and the perturbations for vibrational levels of 2Σ (ν' ≥1) and 1Δ (ν' ≥0) states are analyzed. Finally, the transition properties of five transitions are predicted, including the Franck-Condon Factors (FCFs), transition dipole moments (TDMs), and the spontaneous radiative lifetimes of lower vibrational states. This study will improve our comprehension on the detailed electronic structure and spectroscopy of GeH radical cation.
在本文中，我们采用组态相互作用方法对GeH的电子态进行了高水平的从头算计算。计算中考虑了自旋轨道耦合（SOC）、芯价相关（CV）、标量相对论效应以及戴维森校正（+Q）。得到了与四个最低解离极限相关的13个Λ-S势能曲线（PECs）以及由这些Λ-S态产生的32个Ω电子态。我们的结果表明，第一Σ态和第二Π态与解离极限Ge(P)+H(S)绝热相关，这与先前报道的Ge(P)+H(S)不同。根据计算得到的PECs，确定了Λ-S和Ω态的光谱常数，与先前的实验结果吻合良好。还研究了Λ-S电子态的偶极矩（DMs）。借助涉及1Σ和2Π态的自旋轨道耦合矩阵，揭示了与交叉态相关的复杂耦合，并分析了1Σ态ν'≥0振动能级的弱预解离以及2Σ（ν'≥1）和1Δ（ν'≥0）态振动能级的微扰。最后，预测了五个跃迁的跃迁性质，包括弗兰克-康登因子（FCFs）、跃迁偶极矩（TDMs）以及较低振动态的自发辐射寿命。这项研究将增进我们对GeH自由基阳离子详细电子结构和光谱的理解。
