Nonequilibrated energy distribution in polyatomic molecules: The infrared MPD of cyclobutanone

Article abstract of DOI:10.1063/1.445890

The TEA CO2 infrared MPD of cyclobutanone, on irradiation of the v₂₄ fundamental mode, has been investigated as a function of incident fluence F_i, wavelength and pressure.Dissociation proceeds via two molecular routes; the first yields ethylene plus ketene CH2CO, and the second cyclopropanone and CO plus minor amounts of propylene.The branching ratio R<*>/ increases dramatically at pressure less than ca. 3 Torr from the high pressure thermal limit.This nonthermal feature is most pronounced at low F_i.The average number of quanta abrosbed per molecule , measured by pyroelectric and optoacoustic detection, is independent of cyclobutanone pressure between 0.1 and 10.0 Torr. varies linearly with F_i in the range investigated 0.2-2.0 J cm^-2.An explicit formulation of the infrared MPD process is presented based on a truncated s-fold degenerate harmonic oscillator approach.Vibrational energy transfer is incorporated via v-v bimolecular collisions.The predicted dependence of R on pressure is in good agreement with the experimental data presented herein.Moreover, the observed linear dependence of with F_i, and its independence with respect of pressure, is also borne out by this theory.

Full text of DOI:10.1063/1.445890

Nonequilibrated energy distribution in polyatomic molecules: The infrared MPD of
cyclobutanone
Phillip John, Mark R. Humphries, Robert G. Harrison, and Philip G. Harper
Citation: The Journal of Chemical Physics 79, 1353 (1983); doi: 10.1063/1.445890
View online: http://dx.doi.org/10.1063/1.445890
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/79/3?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:
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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:
128.180.142.23 On: Sat, 13 Dec 2014 13:02:52

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:
128.180.142.23 On: Sat, 13 Dec 2014 13:02:52

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:
128.180.142.23 On: Sat, 13 Dec 2014 13:02:52

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:
128.180.142.23 On: Sat, 13 Dec 2014 13:02:52

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:
128.180.142.23 On: Sat, 13 Dec 2014 13:02:52

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:
128.180.142.23 On: Sat, 13 Dec 2014 13:02:52