邻二氯苯激发态动力学

doi:10.3866/PKU.WHXB201506291

Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (9): 1655-1661.doi: 10.3866/PKU.WHXB201506291

• THERMODYNAMICS, KINETICS, AND STRUCTURAL CHEMISTRY • Previous Articles Next Articles

Dynamics of Excited o-Dichlorobenzene

Xiao-Ying. LI¹,Li. WANG^2,*(),Yan-Qiu. WANG³,Zhe. SONG¹,Ben-Kang. LIU^3,*()

¹ School of Physics and Electronic Technology, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China
² College of Physics and Materials Engineering, Dalian Nationalities University, Dalian 116600, Liaoning Province, P. R. China
³ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China

Received:2015-04-07 Published:2015-09-06
Contact: Li. WANG,Ben-Kang. LIU E-mail:liwangye@dlnu.edu.cn;liubk@dicp.ac.cn
Supported by:
the National Natural Science Foundation of China(21303199)

Abstract

Abstract:

The dynamics of the first excited singlet electronic state (S₁) of o-dichlorobenzene was investigated in real time by the femtosecond pump-probe method combined with time-of-flight mass spectroscopy and the photoelectron velocity mapping technique. The lifetime of the S₁ vibrational ground state was determined experimentally to be (651 ± 10) ps, corresponding to the intersystem crossing process from the S₁ state to the triplet state. Two decay channels were found in the S₁ vibrationally excited mode 9a₂18a₂. The fast process (lifetime constant (458 ± 12) fs) is because of the internal conversion from the S₁ vibrationally excited mode to the highly vibrationally excited ground state (S₀). The slow process (lifetime constant (90 ± 10) ps) is attributed to the intersystem crossing process from the S₁ state to the triplet state (T₁). Photoelectrons with long lifetime characteristics in the spectrum might be connected with the intersystem crossing process. Enhanced spinorbital coupling in the S₁ highly vibrationally excited state accelerates the intersystem crossing process.

Key words: o-Dichlorobenzene, Vibrational excitation, Photoelectron imaging, Photoelectron kinetic energy spectrum

Xiao-Ying. LI,Li. WANG,Yan-Qiu. WANG,Zhe. SONG,Ben-Kang. LIU. Dynamics of Excited o-Dichlorobenzene[J]. Acta Phys. -Chim. Sin. 2015, 31(9), 1655-1661. doi: 10.3866/PKU.WHXB201506291

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Dynamics of Excited o-Dichlorobenzene

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