DFT simulation of the heteroannelated octatetraenes vibronic spectra with the Franck-Condon and Herzberg-Teller approaches including Duschinsky effect

Nataliya N. Karaush, Rashid R. Valiev, Gleb V. Baryshnikov, Boris F. Minaev, Hans Ågren

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Calculations of vibronic structure in the electronic absorption spectra are carried out for the series of heteroannelated octatetraenes on the basis of density functional theory method. Both Franck-Condon and Herzberg-Teller approaches have been used for estimation of frequency and intensity of vibronic bands in the simulated absorption spectra with respect to the S<inf>0</inf> → S<inf>1</inf> electronic transition. The key result discussed in this work is that the electronic transition into the first singlet excited states is vibronically-active in the absorption spectra for all studied circulenes in a good agreement with experimental observations. We have confirmed our previous assumption that the first (low-lying) weak absorption maximum in the spectra of tetra-tert-butyltetraoxa[8]circulene and dithieno[3,4-b:3′,4′-d]thiophene-annelated cyclooctatetraene can be assigned just for the S<inf>0</inf> → S<inf>1</inf> transition which produce the next more intense vibronic satellite. In the case of aza[8]circulenes the S<inf>0</inf> → S<inf>1</inf> transition is symmetry allowed and the corresponding vibronic bands are less intense relative to 0-0 band.

Original languageEnglish
Article number9385
Pages (from-to)65-71
Number of pages7
JournalChemical Physics
Volume459
DOIs
Publication statusPublished - 8 Aug 2015

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Discrete Fourier transforms
Absorption spectra
absorption spectra
Thiophenes
simulation
Electron transitions
Excited states
Density functional theory
thiophenes
electronics
electronic spectra
Satellites
density functional theory
symmetry
excitation

Keywords

  • Circulene
  • Franck-Condon factor
  • Herzberg-Teller approximation
  • Heteroannelated octatetraenes
  • Shpolsky spectra
  • Vibronic effects

ASJC Scopus subject areas

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

Cite this

DFT simulation of the heteroannelated octatetraenes vibronic spectra with the Franck-Condon and Herzberg-Teller approaches including Duschinsky effect. / Karaush, Nataliya N.; Valiev, Rashid R.; Baryshnikov, Gleb V.; Minaev, Boris F.; Ågren, Hans.

In: Chemical Physics, Vol. 459, 9385, 08.08.2015, p. 65-71.

Research output: Contribution to journalArticle

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abstract = "Calculations of vibronic structure in the electronic absorption spectra are carried out for the series of heteroannelated octatetraenes on the basis of density functional theory method. Both Franck-Condon and Herzberg-Teller approaches have been used for estimation of frequency and intensity of vibronic bands in the simulated absorption spectra with respect to the S0 → S1 electronic transition. The key result discussed in this work is that the electronic transition into the first singlet excited states is vibronically-active in the absorption spectra for all studied circulenes in a good agreement with experimental observations. We have confirmed our previous assumption that the first (low-lying) weak absorption maximum in the spectra of tetra-tert-butyltetraoxa[8]circulene and dithieno[3,4-b:3′,4′-d]thiophene-annelated cyclooctatetraene can be assigned just for the S0 → S1 transition which produce the next more intense vibronic satellite. In the case of aza[8]circulenes the S0 → S1 transition is symmetry allowed and the corresponding vibronic bands are less intense relative to 0-0 band.",
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AU - Valiev, Rashid R.

AU - Baryshnikov, Gleb V.

AU - Minaev, Boris F.

AU - Ågren, Hans

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AB - Calculations of vibronic structure in the electronic absorption spectra are carried out for the series of heteroannelated octatetraenes on the basis of density functional theory method. Both Franck-Condon and Herzberg-Teller approaches have been used for estimation of frequency and intensity of vibronic bands in the simulated absorption spectra with respect to the S0 → S1 electronic transition. The key result discussed in this work is that the electronic transition into the first singlet excited states is vibronically-active in the absorption spectra for all studied circulenes in a good agreement with experimental observations. We have confirmed our previous assumption that the first (low-lying) weak absorption maximum in the spectra of tetra-tert-butyltetraoxa[8]circulene and dithieno[3,4-b:3′,4′-d]thiophene-annelated cyclooctatetraene can be assigned just for the S0 → S1 transition which produce the next more intense vibronic satellite. In the case of aza[8]circulenes the S0 → S1 transition is symmetry allowed and the corresponding vibronic bands are less intense relative to 0-0 band.

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