Michael Lucas, Jasmine Minor, Jingsong Zhang, Christopher Brazier. H-atom Dissociation Channels in Ultraviolet Photochemistry of m-PyridylRadical[J]. Chinese Journal of Chemical Physics , 2014, 27(6): 621-627. doi: 10.1063/1674-0068/27/06/621-627
Citation: Michael Lucas, Jasmine Minor, Jingsong Zhang, Christopher Brazier. H-atom Dissociation Channels in Ultraviolet Photochemistry of m-PyridylRadical[J]. Chinese Journal of Chemical Physics , 2014, 27(6): 621-627. doi: 10.1063/1674-0068/27/06/621-627

H-atom Dissociation Channels in Ultraviolet Photochemistry of m-PyridylRadical

doi: 10.1063/1674-0068/27/06/621-627
  • Received Date: 2014-09-08
  • The H atom production channels in the ultraviolet (UV) photochemistry of m-pyridyl radical (m-C5H4N) were investigated at excitation wavelengths from 224 nm to 248 nm by high-n Rydberg atom time-of-flight (HRTOF) technique. The photofragment yield (PFY) spectrum of the H atoms indicates a broad UV absorption feature near 234 nm. The product kinetic energy release is small; the average product kinetic energy at the wavelengths from 224 nm to 248 nm is 0.12 to 0.19 of the maximum excess energy (assuming the lowest energy product channel, H+cyanovinylacetylene). The product kinetic energy distributions are consistent with the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne product channels, with H cyanovinylacetylene as the main H-loss channel. The angular distributions of the H-atom products are isotropic. After the UV electronic excitation, the m-pyridyl radical undergoes internal conversion to the ground electronic state and then unimolecular dissoci-ation to the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne products. The dissociation mechanism of the m-pyridyl radical is similar to that of the o-pyridyl radical reported in the early study.
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    沈阳化工大学材料科学与工程学院 沈阳 110142

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H-atom Dissociation Channels in Ultraviolet Photochemistry of m-PyridylRadical

doi: 10.1063/1674-0068/27/06/621-627

Abstract: The H atom production channels in the ultraviolet (UV) photochemistry of m-pyridyl radical (m-C5H4N) were investigated at excitation wavelengths from 224 nm to 248 nm by high-n Rydberg atom time-of-flight (HRTOF) technique. The photofragment yield (PFY) spectrum of the H atoms indicates a broad UV absorption feature near 234 nm. The product kinetic energy release is small; the average product kinetic energy at the wavelengths from 224 nm to 248 nm is 0.12 to 0.19 of the maximum excess energy (assuming the lowest energy product channel, H+cyanovinylacetylene). The product kinetic energy distributions are consistent with the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne product channels, with H cyanovinylacetylene as the main H-loss channel. The angular distributions of the H-atom products are isotropic. After the UV electronic excitation, the m-pyridyl radical undergoes internal conversion to the ground electronic state and then unimolecular dissoci-ation to the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne products. The dissociation mechanism of the m-pyridyl radical is similar to that of the o-pyridyl radical reported in the early study.

Michael Lucas, Jasmine Minor, Jingsong Zhang, Christopher Brazier. H-atom Dissociation Channels in Ultraviolet Photochemistry of m-PyridylRadical[J]. Chinese Journal of Chemical Physics , 2014, 27(6): 621-627. doi: 10.1063/1674-0068/27/06/621-627
Citation: Michael Lucas, Jasmine Minor, Jingsong Zhang, Christopher Brazier. H-atom Dissociation Channels in Ultraviolet Photochemistry of m-PyridylRadical[J]. Chinese Journal of Chemical Physics , 2014, 27(6): 621-627. doi: 10.1063/1674-0068/27/06/621-627

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