Vibrational analysis and excited-state geometric changes of betaine-30 derived from Raman and infrared spectra combined with ab initio calculations

Sebastian Wachsmann-Hogiu, J. Dreyer, M. Pfeiffer, K. W. Brzezinka, W. Werncke

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

We present a combined experimental and theoretical study of vibrational modes and excited-state geometry changes of betaine-30 (B-30). Infrared and Raman spectra were recorded under electronic off-resonant excitation conditions and also in resonance with the charge transfer transition of B-30. Comparing these spectra with the corresponding vibrational patterns calculated by Hartree-Fock methods we obtained the assignments of the vibrational modes. Excited-state geometry changes were calculated for a smaller model system of B-30 using configuration interaction with single excitations. The calculations predict that the central phenoxide and pyridinium rings move from a twisted conformation in the electronic ground state into a perpendicular position in the first excited state. In addition, the pyridinium ring tilts and the nitrogen atom becomes pyramidalized. In correspondence, we measured two strong low-wavenumber Raman bands with large origin shifts at 291 and 133 cm-1. They were assigned to N-inversion and torsional vibrational modes and are expected to mediate the excited state and back-electron transfer reaction of B-30. Copyright (C) 2000 John Wiley And Sons, Ltd.

Original languageEnglish (US)
Pages (from-to)797-803
Number of pages7
JournalJournal of Raman Spectroscopy
Volume31
Issue number8-9
StatePublished - 2000
Externally publishedYes

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Betaines
Betaine
Excited states
Infrared radiation
Geometry
Ground state
Conformations
Charge transfer
Raman scattering
Nitrogen
Atoms
Electrons

ASJC Scopus subject areas

  • Spectroscopy

Cite this

Vibrational analysis and excited-state geometric changes of betaine-30 derived from Raman and infrared spectra combined with ab initio calculations. / Wachsmann-Hogiu, Sebastian; Dreyer, J.; Pfeiffer, M.; Brzezinka, K. W.; Werncke, W.

In: Journal of Raman Spectroscopy, Vol. 31, No. 8-9, 2000, p. 797-803.

Research output: Contribution to journalArticle

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AU - Wachsmann-Hogiu, Sebastian

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AU - Brzezinka, K. W.

AU - Werncke, W.

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N2 - We present a combined experimental and theoretical study of vibrational modes and excited-state geometry changes of betaine-30 (B-30). Infrared and Raman spectra were recorded under electronic off-resonant excitation conditions and also in resonance with the charge transfer transition of B-30. Comparing these spectra with the corresponding vibrational patterns calculated by Hartree-Fock methods we obtained the assignments of the vibrational modes. Excited-state geometry changes were calculated for a smaller model system of B-30 using configuration interaction with single excitations. The calculations predict that the central phenoxide and pyridinium rings move from a twisted conformation in the electronic ground state into a perpendicular position in the first excited state. In addition, the pyridinium ring tilts and the nitrogen atom becomes pyramidalized. In correspondence, we measured two strong low-wavenumber Raman bands with large origin shifts at 291 and 133 cm-1. They were assigned to N-inversion and torsional vibrational modes and are expected to mediate the excited state and back-electron transfer reaction of B-30. Copyright (C) 2000 John Wiley And Sons, Ltd.

AB - We present a combined experimental and theoretical study of vibrational modes and excited-state geometry changes of betaine-30 (B-30). Infrared and Raman spectra were recorded under electronic off-resonant excitation conditions and also in resonance with the charge transfer transition of B-30. Comparing these spectra with the corresponding vibrational patterns calculated by Hartree-Fock methods we obtained the assignments of the vibrational modes. Excited-state geometry changes were calculated for a smaller model system of B-30 using configuration interaction with single excitations. The calculations predict that the central phenoxide and pyridinium rings move from a twisted conformation in the electronic ground state into a perpendicular position in the first excited state. In addition, the pyridinium ring tilts and the nitrogen atom becomes pyramidalized. In correspondence, we measured two strong low-wavenumber Raman bands with large origin shifts at 291 and 133 cm-1. They were assigned to N-inversion and torsional vibrational modes and are expected to mediate the excited state and back-electron transfer reaction of B-30. Copyright (C) 2000 John Wiley And Sons, Ltd.

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