Direct vs complex reaction dynamics for F+OH->HF+O

Article abstract of DOI:10.1063/1.442167

The exerogicity of the reaction F+H2O->HF+OH is sufficient to give HF(ν'<*>1); howerver, arrested relaxation infrared chemiluminescence experiments on this system show emission from HF(ν'<*>3).The higher vibrational levels are populated by the secondary reaction F(²P)+OH(²II)->HF(¹Σ⁺)+O(³P).By a combination of SCF-Cl calculations and a rotated Morse curve fitting procedure, it is shown that barrier heights on triplet surfaces which correlate reactants and products of the secondary reaction are too high to provide a reaction path.Instead, the reaction proceeds on a singlet surface to produce an HOF complex, followed by rearrangement and a nonadiabatic transition to the triplet surface.An exit-channel barrier results from the surface crossing.The chemiluminescence data are shown to be in accord with this reaction mechanism.

Full text of DOI:10.1063/1.442167

Direct vs complex reaction dynamics for F+OH→HF+O
J. J. Sloan, D. G. Watson, J. M. Williamson, and James S. Wright
Citation: The Journal of Chemical Physics 75, 1190 (1981); doi: 10.1063/1.442167
View online: http://dx.doi.org/10.1063/1.442167
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/75/3?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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25

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:
130.18.123.11 On: Tue, 23 Dec 2014 17:42:25