Effect of conical intersection of benzene on non-adiabatic dynamics

doi:10.1088/1674-1056/ac5607

中国物理B ›› 2022, Vol. 31 ›› Issue (8): 83103-083103.doi: 10.1088/1674-1056/ac5607

Effect of conical intersection of benzene on non-adiabatic dynamics

Duo-Duo Li(李多多)^1,2 and Song Zhang(张嵩)^1,2,†

1 State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China;
2 University of Chinese Academy of Sciences, Beijing 100049, China

收稿日期:2021-12-07 修回日期:2022-02-05 接受日期:2022-02-17 出版日期:2022-07-18 发布日期:2022-07-23
通讯作者: Song Zhang E-mail:zhangsong@wipm.ac.cn
基金资助:
Project supported by the National Key Research and Development Program of China (Grant No. 2019YFA0307700) and the National Natural Science Foundation of China (Grant Nos. 11974381, 11674355, and 21773299).

Effect of conical intersection of benzene on non-adiabatic dynamics

Duo-Duo Li(李多多)^1,2 and Song Zhang(张嵩)^1,2,†

1 State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China;
2 University of Chinese Academy of Sciences, Beijing 100049, China

Received:2021-12-07 Revised:2022-02-05 Accepted:2022-02-17 Online:2022-07-18 Published:2022-07-23
Contact: Song Zhang E-mail:zhangsong@wipm.ac.cn
Supported by:
Project supported by the National Key Research and Development Program of China (Grant No. 2019YFA0307700) and the National Natural Science Foundation of China (Grant Nos. 11974381, 11674355, and 21773299).

摘要/Abstract

摘要： The effect of conical intersection on the excited dynamics of benzene is studied by ab initio theory of electronic structure, which provides an important insight into photophysical and photochemical reactions. Based on the CASSCF(6,6)/6-31+G(d, p) method, the topological structures of conical intersections S₁/S and S₂/S₁ of benzene, as well as the optimal structures of the ground state (S) and excited states (S₁, S₂), are determined. The energy minima of the S₁ state and S₂ state are estimated at 4.608 eV and 6.889 eV, respectively. In addition, the energy values of the conical intersections of S₁/S and S₂/S₁ are predicted to be 5.600 eV and 6.774 eV. According to the topological structures and energy values of the S₂/S₁ and S₁/S conical intersections, the photophysical behavior of benzene excited to the S₂ state and the effects of the S₂/S₁ and S₁/S conical intersections are discussed in detail.

关键词: conical intersection, nonadiabatic dynamics, ultrafast relaxation, quantum chemical calculations

Abstract: The effect of conical intersection on the excited dynamics of benzene is studied by ab initio theory of electronic structure, which provides an important insight into photophysical and photochemical reactions. Based on the CASSCF(6,6)/6-31+G(d, p) method, the topological structures of conical intersections S₁/S and S₂/S₁ of benzene, as well as the optimal structures of the ground state (S) and excited states (S₁, S₂), are determined. The energy minima of the S₁ state and S₂ state are estimated at 4.608 eV and 6.889 eV, respectively. In addition, the energy values of the conical intersections of S₁/S and S₂/S₁ are predicted to be 5.600 eV and 6.774 eV. According to the topological structures and energy values of the S₂/S₁ and S₁/S conical intersections, the photophysical behavior of benzene excited to the S₂ state and the effects of the S₂/S₁ and S₁/S conical intersections are discussed in detail.

Key words: conical intersection, nonadiabatic dynamics, ultrafast relaxation, quantum chemical calculations

中图分类号: (Surface crossings, non-adiabatic couplings)

31.50.Gh

31.15.xv (Molecular dynamics and other numerical methods) 31.70.Hq (Time-dependent phenomena: excitation and relaxation processes, and reaction rates) 31.15.vq (Electron correlation calculations for polyatomic molecules)

Duo-Duo Li(李多多) and Song Zhang(张嵩). Effect of conical intersection of benzene on non-adiabatic dynamics[J]. 中国物理B, 2022, 31(8): 83103-083103.

Duo-Duo Li(李多多) and Song Zhang(张嵩). Effect of conical intersection of benzene on non-adiabatic dynamics[J]. Chin. Phys. B, 2022, 31(8): 83103-083103.

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Effect of conical intersection of benzene on non-adiabatic dynamics

Effect of conical intersection of benzene on non-adiabatic dynamics

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