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

Dynamics of Excited o-Dichlorobenzene

1.
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 Date: 7 April 2015
Available Online: 29 June 2015
Fund Project: 国家自然科学基金(21303199)资助项目 (21303199)

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.
- o-Dichlorobenzene,
- Vibrational excitation,
- Photoelectron imaging,
- Photoelectron kinetic energy spectrum
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