Overtone-induced isomerization of allyl isocyanide

Article abstract of DOI:10.1063/1.455580

The rate of isomerization of allyl isocyanide to allyl cyanide is monitored using Stern-Volmer kinetics when various features of the 5-O and 6-O C-H overtone stretch region are excited.Previously, Reddy and Berry found that the isomerization rates varied from band to band and that the variations were not monotonic with excitation energy.They attributed this behavior to nonstatistical effects.It is found in this study that the isomerization rates vary within an overtone band by up to a factor of 1.8, in addition to the variations from band to band seen previously.This observation rules out the possibility that the overtone bands are purely lifetime broadened.In addition, the photoisomerization rate increases with increasing temperature.An increase of 60 K increases the photolysis yield in the 5-O C-H region by a factor of 3-4, while increases in the 6-O C-H region are smaller, 25percent-60percent.These effects can be qualitatively explained if the overtone spectrum of allyl isocyanide is inhomogeneously broadened because of the presence of vibrational "hot bands." In this case, molecules excited by the photolysis laser will have varying amounts of initial thermal energy depending on where the laser is tuned within a band.A simple model for the effects of hot bands on the isomerization rate is in good agreement with experimental results.It is not necessary to invoke nonstatistical effects in order to explain the observed overtone-pumped isomerization rates of allyl isocyanide.

Full text of DOI:10.1063/1.455580

Overtoneinduced isomerization of allyl isocyanide
Jeffrey Segall and Richard N. Zare
Citation: J. Chem. Phys. 89, 5704 (1988); doi: 10.1063/1.455580
View online: http://dx.doi.org/10.1063/1.455580
View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v89/i9
Published by the AIP Publishing LLC.
Additional information on J. Chem. Phys.
Journal Homepage: http://jcp.aip.org/
Journal Information: http://jcp.aip.org/about/about_the_journal
Top downloads: http://jcp.aip.org/features/most_downloaded
Information for Authors: http://jcp.aip.org/authors
Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions

Downloaded 07 Oct 2013 to 128.252.67.66. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions