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 S_(1)/S and S_(2)/S_(1)of benzene,as well as the optimal structures of the ground state(S)and excited states(S_(1),S_(2)),are determined.The energy minima of the S_(1)state and S_(2)state are estimated at 4.608 e V and 6.889 e V,respectively.In addition,the energy values of the conical intersections of S_(1)/S and S_(2)/S_(1)are predicted to be 5.600 e V and 6.774 e V.According to the topological structures and energy values of the S_(2)/S_(1)and S_(1)/S conical intersections,the photophysical behavior of benzene excited to the S_(2)state and the effects of the S_(2)/S_(1)and S_(1)/S conical intersections are discussed in detail.
作者
Duo-Duo Li
Song Zhang
李多多;张嵩(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;University of Chinese Academy of Sciences,Beijing 100049,China)
基金
Project supported by the National Key Research and Development Program of China(Grant No.2019YFA0307700)
the National Natural Science Foundation of China(Grant Nos.11974381,11674355,and 21773299)。
