### 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 2^{1} 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 2^{1}A_{g} states grow larger towards the direction of the C-C stretching mode with increasing N.

Original language | English |
---|---|

Article number | 174313 |

Journal | Journal of Chemical Physics |

Volume | 131 |

Issue number | 17 |

DOIs | |

Publication status | Published - Nov 17 2009 |

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### All Science Journal Classification (ASJC) codes

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

### Cite this

*Journal of Chemical Physics*,

*131*(17), [174313]. https://doi.org/10.1063/1.3261729

**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.

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 131, no. 17, 174313. https://doi.org/10.1063/1.3261729

}

TY - JOUR

T1 - Ab initio study of the excited singlet states of all-trans α,ω -diphenylpolyenes with one to seven polyene double bonds

T2 - Simulation of the spectral data within Franck-Condon approximation

AU - Mizukami, Wataru

AU - Kurashige, Yuki

AU - Ehara, Masahiro

AU - Yanai, Takeshi

AU - Itoh, Takao

PY - 2009/11/17

Y1 - 2009/11/17

N2 - 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.

AB - 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.

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U2 - 10.1063/1.3261729

DO - 10.1063/1.3261729

M3 - Article

VL - 131

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

M1 - 174313

ER -