A quantum mechanical, time-dependent wave packet interpretation of the diffuse structures in the S0 --> S1 absorption spectrum of FNO: Coexistence of direct and indirect dissociation

Article abstract of DOI:10.1063/1.462886

We have investigated the photodissociation of FNO in the first absorption band (S₀ --> S₁) by a two-dimensional wave packet study based on an ab initio potential energy surface.The quantum chemical calculations were performed in the multiconfiguration self-consistent field (MCSCF) approach including the N-O and the F-NO bond distances with the FNO bond angle being fixed.The most striking feature of the time-dependent dynamical analysis is a bifurcation of the wave packet near the Franck-Condon point: while one part of the wave packet leaves the inner region of the potential energy surface very rapidly, a second part remains trapped for several periods in an extremely shallow well at short F-NO distances.The direct part leads to a broad background in the absorption spectrum while the trapped portion of the wave packet gives rise to relatively narrow resonances, i.e., well resolved diffuse vibrational structures.The bandwidth decreases with the degree of internal excitation.The calculated spectrum agrees well with the measured one.

Full text of DOI:10.1063/1.462886

A quantum mechanical, timedependent wave packet interpretation of the diffuse
structures in the S 0S 1 absorption spectrum of FNO: Coexistence of direct and
indirect dissociation
Hans Ulrich Suter, J. Robert Huber, Michael von Dirke, Agathe Untch, and Reinhard Schinke
Citation: The Journal of Chemical Physics 96, 6727 (1992); doi: 10.1063/1.462886
View online: http://dx.doi.org/10.1063/1.462886
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:
217.75.218.194 On: Sat, 24 May 2014 14:31:26

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:
217.75.218.194 On: Sat, 24 May 2014 14:31:26

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:
217.75.218.194 On: Sat, 24 May 2014 14:31:26

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:
217.75.218.194 On: Sat, 24 May 2014 14:31:26

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:
217.75.218.194 On: Sat, 24 May 2014 14:31:26

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:
217.75.218.194 On: Sat, 24 May 2014 14:31:26