Abstract
The photodissociation dynamics of vinyl bromide and perfluorovinyl bromide have been investigated at 234 nm using a photofragment ion imaging technique coupled with a state-selective [2+1] resonance-enhanced multiphoton ionization scheme. The nascent Br atoms stem from the primary C-Br bond dissociation leading to the formation of C 2H 3(X̃) and Br( 2P j;j=1/2,3/2). The obtained translational energy distributions have been well fitted by a single Boltzmann and three Gaussian functions. Boltzmann component has not been observed in the perfluorovinyl bromide. The repulsive 3A ′(n, σ *) state has been considered as the origin of the highest Gaussian components. Middle translational energy components with Gaussian shapes are produced from the 1A ″(π, σ *) and/or 3A ″(π, σ *) which are very close in energy. Low-energy Gaussian components are produced via predissociation from the 3A ′(π,π *) state. The assignments have also been supported by the recoil anisotropy corresponding to the individual components. It is suggested that intersystem crossing from the triplet states to the ground state has been attributed to the Boltzmann component and the fluorination reduces the probability of this electronic relaxation process.
| Original language | English |
|---|---|
| Article number | 034308 |
| Journal | Journal of Chemical Physics |
| Volume | 122 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - 2005 Aug 8 |
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All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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The dynamics of Br( 2P j) formation in the photodissociation of vinyl and perfluorovinyl bromides. / Lee, Kyoung Seok; Lee, Keon Woo; Kim, Tae Kyu; Ryoo, Ryong; Jung, Kyung Hoon.
In: Journal of Chemical Physics, Vol. 122, No. 3, 034308, 08.08.2005.Research output: Contribution to journal › Article
TY - JOUR
T1 - The dynamics of Br( 2P j) formation in the photodissociation of vinyl and perfluorovinyl bromides
AU - Lee, Kyoung Seok
AU - Lee, Keon Woo
AU - Kim, Tae Kyu
AU - Ryoo, Ryong
AU - Jung, Kyung Hoon
PY - 2005/8/8
Y1 - 2005/8/8
N2 - The photodissociation dynamics of vinyl bromide and perfluorovinyl bromide have been investigated at 234 nm using a photofragment ion imaging technique coupled with a state-selective [2+1] resonance-enhanced multiphoton ionization scheme. The nascent Br atoms stem from the primary C-Br bond dissociation leading to the formation of C 2H 3(X̃) and Br( 2P j;j=1/2,3/2). The obtained translational energy distributions have been well fitted by a single Boltzmann and three Gaussian functions. Boltzmann component has not been observed in the perfluorovinyl bromide. The repulsive 3A ′(n, σ *) state has been considered as the origin of the highest Gaussian components. Middle translational energy components with Gaussian shapes are produced from the 1A ″(π, σ *) and/or 3A ″(π, σ *) which are very close in energy. Low-energy Gaussian components are produced via predissociation from the 3A ′(π,π *) state. The assignments have also been supported by the recoil anisotropy corresponding to the individual components. It is suggested that intersystem crossing from the triplet states to the ground state has been attributed to the Boltzmann component and the fluorination reduces the probability of this electronic relaxation process.
AB - The photodissociation dynamics of vinyl bromide and perfluorovinyl bromide have been investigated at 234 nm using a photofragment ion imaging technique coupled with a state-selective [2+1] resonance-enhanced multiphoton ionization scheme. The nascent Br atoms stem from the primary C-Br bond dissociation leading to the formation of C 2H 3(X̃) and Br( 2P j;j=1/2,3/2). The obtained translational energy distributions have been well fitted by a single Boltzmann and three Gaussian functions. Boltzmann component has not been observed in the perfluorovinyl bromide. The repulsive 3A ′(n, σ *) state has been considered as the origin of the highest Gaussian components. Middle translational energy components with Gaussian shapes are produced from the 1A ″(π, σ *) and/or 3A ″(π, σ *) which are very close in energy. Low-energy Gaussian components are produced via predissociation from the 3A ′(π,π *) state. The assignments have also been supported by the recoil anisotropy corresponding to the individual components. It is suggested that intersystem crossing from the triplet states to the ground state has been attributed to the Boltzmann component and the fluorination reduces the probability of this electronic relaxation process.
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U2 - 10.1063/1.1825994
DO - 10.1063/1.1825994
M3 - Article
AN - SCOPUS:22944472746
VL - 122
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 3
M1 - 034308
ER -