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Theory of fluorescence excitation spectra using anharmonic-coriolis coupling in S1 and internal conversion to S0. I. General formalism

Helman, Adam and Marcus, R. A. (1993) Theory of fluorescence excitation spectra using anharmonic-coriolis coupling in S1 and internal conversion to S0. I. General formalism. Journal of Chemical Physics, 99 (7). pp. 5002-5010. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:HELjcp93a

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Abstract

A treatment of one- or two-photon fluorescence excitation spectra is described using the vibration–rotation coupling of zeroth order states in the excited electronic state and nonadiabatic coupling to the ground state. Using perturbation theory, experimental harmonic frequencies, an anharmonic force field, and various theoretical Coriolis coupling constants, a quasistationary molecular eigenstate in an excited electronic state S1 is first calculated. The S1 eigenstate is then coupled via the nonadiabatic nuclear kinetic energy operator (internal conversion) to rovibronic states in the ground state manifold, the latter states approximated in a simple manner. A search algorithm is used to select the S1 dark states and the S0 states. Both the perturbation theory coefficient and the Franck–Condon factors are employed in the evaluation function used in the search. The results are applied in part II to the channel three problem in benzene.


Item Type:Article
Additional Information:Copyright © 1993 American Institute of Physics (Received April 24 1992; accepted 24 June 1993) It is a pleasure to acknowledge the support of this research by the National Science Foundation. This research was supported by the Caltech Consortium in Chemistry and Chemical Engineering; founding members E. I. du Pont de Neumours and Company, Inc., Eastman Kodak Company, and Minnesota Mining and Manufacturing Company. Arthur Amos Noyes Laboratory of Chemical Physics Contribution No. 8604.
Subject Keywords:FLUORESCENCE; EXCITATION; ANHARMONICITY; CORIOLIS FORCE; COUPLING; TWO–PHOTON SPECTRA; VIBRATIONAL STATES; ROTATIONAL STATES; GROUND STATES; PERTURBATION THEORY; EIGENSTATES; KINETIC ENERGY; QUANTUM OPERATORS; FRANCK–CONDON PRINCIPLE; BENZENE
Record Number:CaltechAUTHORS:HELjcp93a
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:HELjcp93a
Alternative URL:http://dx.doi.org/10.1063/1.466002
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5631
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:26 Oct 2006
Last Modified:26 Dec 2012 09:14

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