Configuration interaction investigation including spin-orbit coupling effect for electronic states of IBr and its cation

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• 作者：Rui Li ; Changli Wei ; Qixiang Sun ; Erping Sun ; Mingxing Jin ; Haifeng Xu ; Bing Yan
• 关键词：Iodine monobromide ; MRCI+Q calculation ; Spin&ndash ; orbit coupling ; Potential energy curves ; Low-lying electronic states
• 刊名：Journal of Quantitative Spectroscopy and Radiative Transfer
• 出版年：January, 2014
• 年：2014
• 卷：133
• 期：Complete
• 页码：271-280
• 全文大小：1525 K

文摘

Iodine monobromide (IBr) and its cation (IBr⁺), which play an important role in the stratospheric ozone depletion, have received much attention. However, the electronic states of IBr/IBr⁺ have not been well understood. In this paper, the potential energy curves (PECs) of low-lying electronic states for IBr/IBr⁺ were computed with high-level multireference configuration interaction (MRCI) method. The spin-orbit coupling effect was taken into account via the state interaction method with the full Breit-Pauli Hamiltonian. For IBr, the PECs of 12 螞-S states correlated with the lowest dissociation limit of IBr molecule and 23惟 states generated from those 螞-S states were calculated. The spectroscopic constants of the bound states were obtained, which are consistent with previous experimental results. The two avoided crossing points between (2)0⁺/(3)0⁺ and (3)0⁺/(4)0⁺ were interpreted by analysis of 螞-S compositions of 惟 states at various bond lengths. Based on potential energy curves and transition dipole moments, the radiative lifetime of 1³螤₁ was evaluated. For IBr⁺, the PECs of 12 螞-S states and 4 low-lying 惟 states were calculated, from which the spectroscopic constants were evaluated. Finally, the ionization energies from the neutral ground state (X¹危⁺) to different ionic states (X²螤_3/2, X²螤_1/2, A²螤_3/2 and A²螤_1/2) were obtained.