Ab initio CI calculations on potential energy curves of low-lying states of BrF and its cation including spin-orbit coupling

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• 作者：Rui Li^a ; ^b ; Xiaomei Zhang^a ; Wei Feng^a ; Yuanfei Jiang^a ; Dehou Fei^a ; Mingxing Jin^a ; Bing Yan^a ; ^{yanbing@jlu.edu.cn" class="auth_mail} ; Haifeng Xu^a ; ^{xuhf@jlu.edu.cn" class="auth_mail}
• 关键词：BrF ; Configuration interaction ; Spin&ndash ; orbit coupling ; Potential energy curves ; Ionization energy
• 刊名：Computational and Theoretical Chemistry
• 出版年：15 March, 2014
• 年：2014
• 卷：1032
• 期：Complete
• 页码：20-26
• 全文大小：1009 K

文摘

Bromine monofluoride (BrF) and its cation (BrF⁺) have attracted much scientific attention because of their potential significance in the stratospheric ozone depletion and the development of chemical laser. Despite that the structure and spectroscopic properties of the 1³螤₀₊ (B³螤₀₊) and 1³螤₁ states of BrF have been experimentally investigated in the literature, theoretical investigations of BrF and its cation are relatively sparse. In this paper, the low-lying electronic states for BrF/BrF⁺ were studied by means of relativistic multireference configuration interaction method (including Davidson correction). The spin-orbit coupling effect was considered by the state-interacting method with the full Breit-Pauli Hamiltonian. For BrF, the potential energy curves (PECs) of 12 螞-S states and 23 惟 states generated from the 螞-S states were calculated. The avoided crossing mechanism of 惟 = 0⁺ states were analyzed by the variations of dominant 螞-S composition for 惟 states at several different internuclear distances. For BrF⁺, the PECs of the ground states (X²螤_3/2 and X²螤_1/2) were computed. The spectroscopic constants of the bound states of BrF/BrF⁺ were determined, which are in good agreement with previously available experimental results. Finally, the ionization energies from the neutral ground state (X¹危⁺) to different ionic states (X²螤_3/2, and X²螤_1/2) were obtained.