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Citation: CAO Zhen-Zhou, ZHANG Chang-Hua, WANG Yan-Mei, ZHANG Feng, HUA Lin-Qiang, ZHANG Bing. Photodissociation Dynamics of o-Bromotoluene at 234 and 267 nm[J]. Acta Physico-Chimica Sinica, ;2009, 25(03): 423-429. doi: 10.3866/PKU.WHXB20090305 shu

Photodissociation Dynamics of o-Bromotoluene at 234 and 267 nm

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

Corresponding author: ZHANG Chang-Hua, WANG Yan-Mei, ZHANG Feng, HUA Lin-Qiang, ZHANG Bing, BZhang@wipm.ac.cn
Received Date: 7 October 2008
Available Online: 31 December 2008

The photodissociation of o-bromotoluene was studied at 234 and 267 nm using velocity map imaging combined with a resonance-enhanced multiphoton ionization (REMPI) technique. Translational energy distributions suggested that ground state Br(2P3/2) and spin-orbit excited state Br*(2P1/2) fragments were all generated via two dissociation channels: a fast channel and a slow channel. The anisotropy parameters of the fast channels were determined to be 1.15 (Br) and 0.55 (Br*) at 234 nm, 0.90 (Br) and 0.60 (Br*) at 267 nm. The anisotropy parameters of the slowchannels were 0.12 (Br) and 0.14 (Br*) at 234 nm, 0.11 (Br) and 0.10 (Br*) at 267 nm. The Br and Br*fragments of the slow channel were less anisotropic than those of the fast channel. The total relative quantumyields of Br (Φ(Br)) were 0.67 at 234 nm and 0.70 at 267 nm. Ground state Br(2P3/2) was the main product fromthe photolysis of o-bromotoluene at 234 and 267 nm. We propose that the fast channel originates from excitation of bound excited singlet (π, π*) states followed by predissociation along repulsive (n,σ*) states. The anisotropy parameters of the slowchannelswere close to zero indicating a hot dissociation mechanism on a highly vibrational ground state followed the internal conversion of the excited singlet state.
- Ion velocity imaging,
- Photodissociation,
- o-Bromotoluene
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