Citation: DING Zhong-Hua, QIU Xue-Jun, XU Yan-Qi, WANG Yan-Mei, ZHANG Bing. Ultrafast Internal Conversion Dynamics of Benzyl Chloride by Femtosecond Time-Resolved Photoelectron Imaging[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201210124 shu

Ultrafast Internal Conversion Dynamics of Benzyl Chloride by Femtosecond Time-Resolved Photoelectron Imaging

DING Zhong-Hua ^1,2 ,
QIU Xue-Jun ^1,2 ,
XU Yan-Qi ^1,2 ,
WANG Yan-Mei ^1,2, ,
ZHANG Bing ^1,2

1.
1 State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan, Hubei 430071, P. R. China;
2 University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Received Date: 24 August 2012
Available Online: 12 October 2012
Fund Project: 国家自然科学基金(21173256, 91121006)资助项目 (21173256, 91121006)

The ultrafast internal conversion of benzyl chloride (BzCl) was studied with femtosecond time-resolved photoelectron imaging (TRPEI) coupled with time-resolved mass spectroscopy. Time-energy maps of the photoelectron intensity and the angular anisotropy were generated from a series of photoelectron images. Upon absorption of two 400 nm photons, benzyl chloride was excited to the S₄ and S₂ states at the same time. The time evolution of the parent ion with different pump-probe delays can be well described by biexponential decay. The fit yielded τ₁=50 fs and τ₂=910 fs. By analysis of time-resolved photoelectron kinetic energy distributions, it is concluded that the excited S₄ state has coupled with and decayed to the S₂ state in a short time scale and then converted to the S₁ state through ultrafast internal conversion (IC). Within 50 fs, the molecule electronically relaxes into S₁ through IC and from there, decays to the S₀ ground state with the relatively slow time constant of 910 fs. The anisotropy parameters of photoelectron angular distributions changed from 0.87 at the delay time of 0 fs to 0.94 at 25 fs and then to 0.59 at 190 fs, which also reflects the coupling from the S₄ state to the S₂ state and the following IC to the S₁ state.
- Benzyl chloride,
- Photoelectron imaging,
- Internal conversion,
- Pump-probe,
- Time-resolved spectroscopy
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