An ab initio study on the electronic excited states and photodissociation mechanism of bromocarbene molecule

We used the internally contracted explicitly correlated multireference configuration interaction (icMRCI-F12) method combined with Davidson correction to conduct a high-precision study of CHBr. The spin-orbit coupling (SOC) is incorporated into the calculation. The 21 spin-free states split into 53...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2023-06, Vol.25 (24), p.16414-16422
Main Authors: Shan, Shimin, Sun, ErPing, Gao, Yongquan, Li, Zirun, Xu, Haifeng, Yan, Bing
Format: Article
Language:English
Subjects:
Atomic energy levels
Configuration interaction
Electron states
Hydrogen bonds
Mathematical analysis
Oscillator strengths
Photodissociation
Potential energy
Spin-orbit interactions
Vertical oscillations
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Summary:We used the internally contracted explicitly correlated multireference configuration interaction (icMRCI-F12) method combined with Davidson correction to conduct a high-precision study of CHBr. The spin-orbit coupling (SOC) is incorporated into the calculation. The 21 spin-free states split into 53 spin-coupled states of CHBr. The vertical transition energies and oscillator strengths are obtained of these states. The SOC effect on the equilibrium structures and the harmonic vibrational frequencies of the ground state X A', the lowest triplet state a A'' and the first excited singlet state A A'' is investigated. The results reveal a significant effect of the SOC on the bond angle and the frequency of the bending mode of a A''. The potential energy curves of electronic states of CHBr as functions of the H-C-Br bond angle, C-H bond length, and C-Br bond length, respectively, are also investigated. Based on the calculated results, the interactions between electronic states and photodissociation mechanism involved in CHBr in the ultraviolet region are explored. Our theoretical studies will shed light on the complicated interactions and dynamics of the electronic states of bromocarbenes.
ISSN:1463-9076
1463-9084
DOI:10.1039/d3cp00985h