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Ab initio study of the excited singlet states of all-trans alpha,omega-diphenylpolyenes with one to seven polyene double bonds: Simulation of the spectral data within Franck–Condon approximation

J. Chem. Phys. 131, 174313 (2009); doi:10.1063/1.3261729

Published 6 November 2009

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Wataru Mizukami,1 Yuki Kurashige,1,2 Masahiro Ehara,1,2 Takeshi Yanai,1,2 and Takao Itoh3
1The Graduate University for Advanced Studies, Myodaiji, Okazaki, Aichi 444-8585, Japan
2Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan
3Graduate School of Integrated Arts and Sciences, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima City 739-8521, Japan
Computational simulations of the electronic spectra with ab initio electronic structure calculations are presented for all-trans alpha,omega-diphenylpolyenes with the polyene double bond number (N) from 1 to 7. A direct comparison of the fluorescence spectra of diphenylpolyenes was made between the results of highly accurate calculations and the experimental data for the systems with various chain lengths. For the realistic simulation of the emission, the total vibrational wave function was described approximately as a direct product of one-dimensional (1D) vibrational wave functions along the normal coordinates that are determined from the vibrational analysis of the ground state. The observed spectra can be reproduced in a computationally efficient way by selecting effective C–C and C=C stretching modes for the constructions of the 1D vibrational Hamiltonians. The electronic structure calculations were performed using the multireference Møller–Plesset perturbation theory with complete active space configuration interaction reference functions. Based on the vertical excitation energies computed, the lowest singlet excited state of diphenylbutadiene is shown to be the optically forbidden 2 1Ag state. The simulations of fluorescence spectra involving vibronic coupling effects reveal that the observed strong single C=C band consists of two major degenerate vibrational C=C modes for the shorter diphenylpolyenes with N=3 and 5. Further, the relative intensities of the C–C stretching modes in the fluorescence spectra tend to be larger than those of the C=C stretching modes for the systems with N over 5. This indicates that the geometric differences of the energy minima between the ground (1 1Ag) and 2 1Ag states grow larger towards the direction of the C–C stretching mode with increasing N. ©2009 American Institute of Physics
History: Received 26 August 2009; accepted 20 October 2009; published 6 November 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/174313/1
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KEYWORDS and PACS

Keywords
PACS
  • 71.15.Qe
    Excited states: methodology (condensed matter electronic structure)
  • 61.50.Lt
    Crystal binding; cohesive energy
  • 78.55.Kz
    Photoluminescence in solid organic materials
  • 63.50.-x
    Vibrational states in disordered systems
  • 71.20.Rv
    Electronic structure of polymers and organic compounds
  • YEAR: 2009

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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