Ab initio study of the excited singlet states of all-trans α,ω -diphenylpolyenes with one to seven polyene double bonds

Simulation of the spectral data within Franck-Condon approximation

Wataru Mizukami, Yuki Kurashige, Masahiro Ehara, Takeshi Yanai, Takao Itoh

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Computational simulations of the electronic spectra with ab initio electronic structure calculations are presented for all-trans α,ω -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 21 A g 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 1 A g) and 21Ag states grow larger towards the direction of the C-C stretching mode with increasing N.

Original languageEnglish
Article number174313
JournalJournal of Chemical Physics
Volume131
Issue number17
DOIs
Publication statusPublished - Nov 17 2009

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Polyenes
Excited states
Stretching
Fluorescence
Wave functions
approximation
excitation
Electronic structure
simulation
fluorescence
Hamiltonians
Excitation energy
wave functions
electronic structure
Bond number
Chain length
Ground state
C band
electronic spectra
configuration interaction

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Ab initio study of the excited singlet states of all-trans α,ω -diphenylpolyenes with one to seven polyene double bonds : Simulation of the spectral data within Franck-Condon approximation. / Mizukami, Wataru; Kurashige, Yuki; Ehara, Masahiro; Yanai, Takeshi; Itoh, Takao.

In: Journal of Chemical Physics, Vol. 131, No. 17, 174313, 17.11.2009.

Research output: Contribution to journalArticle

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abstract = "Computational simulations of the electronic spectra with ab initio electronic structure calculations are presented for all-trans α,ω -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 M{\o}ller-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 21 A g 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 1 A g) and 21Ag states grow larger towards the direction of the C-C stretching mode with increasing N.",
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