Dissociation of cyclohexene and 1,4-cyclohexadiene in a molecular beam

Article abstract of DOI:10.1063/1.456841

Molecular-beam photofragmentation translational spectroscopy of cyclohexene and 1,4-cyclohexadiene was carried out using 193 nm and IR multiphoton excitation. At 193 nm, both the retro-Diels-Alder reaction of cyclohexene and H₂ elimination from both molecules were observed in the ground electronic state, indicating the occurrence of internal conversion from the initially excited electronic states. The retro-Diels-Alder reaction is shown to be concerted up to an internal energy higher than 148 kcal/mol. Hydrogen-atom elimination was also observed for both molecules following 193 nm excitation. The H atom is eliminated from an excited state of cyclohexene and is assigned to be from a carbon adjacent to the double bond, with a corresponding C-H bond energy of 87 ± 3 kcal/mol. It is shown that the peak of the translational energy distribution for concerted dissociation in the ground state is determined mainly by the dynamics of the potential-energy release along the reaction coordinate, and is not sensitive to either the amount of internal energy or the form of excitation.

Full text of DOI:10.1063/1.456841

Dissociation of cyclohexene and 1,4cyclohexadiene in a molecular beam
Xinsheng Zhao, Robert E. Continetti, Atsushi Yokoyama, Eric J. Hintsa, and Yuan T. Lee
Citation: The Journal of Chemical Physics 91, 4118 (1989); doi: 10.1063/1.456841
View online: http://dx.doi.org/10.1063/1.456841
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/91/7?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.22.67.107 On: Mon, 24 Nov 2014 12:59:04