Vibrational excitation of the allene-fluorine reaction in cryogenic matrices: Possible mode selectivity

Article abstract of DOI:10.1063/1.444678

The infrared induced reaction of allene (C3H4) and fluorine in N2, Ar, Kr, and Xe matrices at 12 K has been studied.The reaction is promoted by the selective vibrational excitation of C3H4*F2 reactive pairs and the course of the reaction followed by infrared spectroscopy.Four products are detected, consistent with the concerted addition of F2 across the C-C double bond to form vibrationally excited cis- and gauche-CH2CFCH2F which may then eliminate HF to yield either CHCCH2F*HF or CH2=C=CHF*HF pairs.The relative abundance of each product depends markedly upon the matrix.Selective vibrational photoisomerization of CH2=CFCH2F was used to distinguish and assign spectral features due to the cis- and gauche-rotameters as well as to provide evidence about the torsional barrier in the matrix.In a particular matrix, the allene-fluorine reaction product distribution is independent of the exciting frequency, with measurements at 1679, 1953, 1999, and 3076 cm^-1.However, the relative quantum yield at 3076 cm^-1 is three orders of magnitude higher than observed at the lower frequencies.Furthermore, the quantum yields at 1680, 1953, and 1999 cm^-1 show differences that implicate mode selectivity in the allene-fluorine reaction.The CH2 rocking overtone 2ν₉ at 1999 cm^-1 and perhaps as well the CH2 bending overtone 2ν₁₀ at 1679 cm^-1 show a higher reaction propensity than that of the asymmetric skeletal stretching vibration ν₆ at 1953 cm^-1.

Full text of DOI:10.1063/1.444678

Vibrational excitation of the allene–fluorine reaction in cryogenic matrices: Possible
mode selectivity
Arne K. Knudsen and George C. Pimentel
Citation: The Journal of Chemical Physics 78, 6780 (1983); doi: 10.1063/1.444678
View online: http://dx.doi.org/10.1063/1.444678
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/78/11?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:
128.138.73.68 On: Sat, 20 Dec 2014 09:02:38

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:
128.138.73.68 On: Sat, 20 Dec 2014 09:02:38

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:
128.138.73.68 On: Sat, 20 Dec 2014 09:02:38

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:
128.138.73.68 On: Sat, 20 Dec 2014 09:02:38

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:
128.138.73.68 On: Sat, 20 Dec 2014 09:02:38

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:
128.138.73.68 On: Sat, 20 Dec 2014 09:02:38

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:
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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:
128.138.73.68 On: Sat, 20 Dec 2014 09:02:38

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