Mapping of parent transition-state wave functions into product rotations: An experimental and theoretical investigation of the photodissociation of FNO

Article abstract of DOI:10.1063/1.462603

We study experimentally and theoretically reflection-type structures in the rotational distributions of NO following the photodissociation of FNO via excitation of the S₁ state.Exciting quasibound states with zero quanta of bending vibration in the FNO(S₁) state yields Gaussian-type rotational distributions, while excitation of states with one bending quantum leads to bimodal distributions.In the latter case, the ratio of the two intensity maxima depends on the number of NO stretching quanta in the S₁ state.The accompanying calculations employing a three-dimensional ab initio potential energy surface for the S₁ state of FNO are performed in the time-dependent wave packet approach.They reproduce the main features of the experimental distributions, especially the bimodality.The analysis of two-dimensional calculations for a frozen NO bond distance shows that the final rotational state distributions can be explained as the result of a dynamical mapping of the stationary wave function on the transition line onto the fragment rotational quantum number axis.Here the transition line is defined as the line which separates the inner part of the FNO(S₁) potential energy surface from the strongly repulsive F + NO product channel.

Full text of DOI:10.1063/1.462603

Mapping of parent transitionstate wave functions into product rotations: An
experimental and theoretical investigation of the photodissociation of FNO
Amy Ogai, James Brandon, Hanna Reisler, Hans Ulrich Suter, J. Robert Huber, Michael von Dirke, and
Reinhard Schinke
Citation: The Journal of Chemical Physics 96, 6643 (1992); doi: 10.1063/1.462603
View online: http://dx.doi.org/10.1063/1.462603
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/96/9?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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47

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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47

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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47

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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47

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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47

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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47

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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47

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:
205.208.120.157 On: Tue, 16 Dec 2014 04:38:47