Proton-transferring systems studied by vibrational spectroscopy and theoretical ab initio calculations. The S0 and T1 states of [2,2′-bipyridine]-3,3′-diol

A. Mordzinski, K. Kownacki, A. Les, N. A. Oyler, Ludwik Adamowicz, F. W. Langkilde, R. Wilbrandt

Research output: Contribution to journalArticle

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Abstract

Tautomerization and phototautomerization of [2,2′-bipyridine]-3,3′-diol is investigated by means of infrared, Raman, and time-resolved resonance Raman spectroscopies and ab initio theoretical calculations. Full ab initio SCF (self-consistent field method) geometry optimization followed by MBPT (2)/6-31G** (second-order many-body perturbation theory) energy calculations of both tautomeric forms in the ground state and the lowest excited triplet state is reported and discussed. Two tautomeric forms. A (dihydroxy) and B (dioxo) are found to be minima on the S0 and T1 potential energy surfaces. While form A is the most stable one in the ground state, the energetic ordering is reversed when going to the triplet state. A good agreement between the experimental and calculated vibrational spectra allows a reliable assignment of most vibrational bands corresponding to tautomer A in the ground state. To assign the observed triplet-triplet optical transition and estimate intensities of resonance Raman bands in the triplet state, excitation energies and oscillator strengths of higher triplet states relative to T1 are calculated. Tentative assignments for the resonance Raman bands observed in the lowest excited triplet state are given. All observed vibrational bands are assigned to totally symmetric modes of the most stable B form. From a comparison of the observed and calculated T1 resonance Raman spectra, it is concluded that two transitions, namely, T1 → T5 and T1 → T8, contribute to the resonance Raman scattering and to the triplet-triplet absorption band observed around 430 nm. These states are both of Ag symmetry and are calculated at 3.15 (T5) and 4.80 eV (T8) above T1 (Bu). In view of the fact that the exciting wavelength (around 430 nm, 2.88 eV) is substantially out of resonance with the calculated T1 → T8 transition, vibronic coupling between T5 and T8 is considered as a possibility.

Original languageEnglish (US)
Pages (from-to)5212-5220
Number of pages9
JournalJournal of Physical Chemistry
Volume98
Issue number20
StatePublished - 1994
Externally publishedYes

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Vibrational spectroscopy
atomic energy levels
Protons
protons
Ground state
spectroscopy
ground state
Excited states
Raman scattering
Raman spectra
tautomers
resonance scattering
Potential energy surfaces
Optical transitions
optical transition
Excitation energy
oscillator strengths
vibrational spectra
Vibrational spectra
self consistent fields

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Proton-transferring systems studied by vibrational spectroscopy and theoretical ab initio calculations. The S0 and T1 states of [2,2′-bipyridine]-3,3′-diol. / Mordzinski, A.; Kownacki, K.; Les, A.; Oyler, N. A.; Adamowicz, Ludwik; Langkilde, F. W.; Wilbrandt, R.

In: Journal of Physical Chemistry, Vol. 98, No. 20, 1994, p. 5212-5220.

Research output: Contribution to journalArticle

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title = "Proton-transferring systems studied by vibrational spectroscopy and theoretical ab initio calculations. The S0 and T1 states of [2,2′-bipyridine]-3,3′-diol",
abstract = "Tautomerization and phototautomerization of [2,2′-bipyridine]-3,3′-diol is investigated by means of infrared, Raman, and time-resolved resonance Raman spectroscopies and ab initio theoretical calculations. Full ab initio SCF (self-consistent field method) geometry optimization followed by MBPT (2)/6-31G** (second-order many-body perturbation theory) energy calculations of both tautomeric forms in the ground state and the lowest excited triplet state is reported and discussed. Two tautomeric forms. A (dihydroxy) and B (dioxo) are found to be minima on the S0 and T1 potential energy surfaces. While form A is the most stable one in the ground state, the energetic ordering is reversed when going to the triplet state. A good agreement between the experimental and calculated vibrational spectra allows a reliable assignment of most vibrational bands corresponding to tautomer A in the ground state. To assign the observed triplet-triplet optical transition and estimate intensities of resonance Raman bands in the triplet state, excitation energies and oscillator strengths of higher triplet states relative to T1 are calculated. Tentative assignments for the resonance Raman bands observed in the lowest excited triplet state are given. All observed vibrational bands are assigned to totally symmetric modes of the most stable B form. From a comparison of the observed and calculated T1 resonance Raman spectra, it is concluded that two transitions, namely, T1 → T5 and T1 → T8, contribute to the resonance Raman scattering and to the triplet-triplet absorption band observed around 430 nm. These states are both of Ag symmetry and are calculated at 3.15 (T5) and 4.80 eV (T8) above T1 (Bu). In view of the fact that the exciting wavelength (around 430 nm, 2.88 eV) is substantially out of resonance with the calculated T1 → T8 transition, vibronic coupling between T5 and T8 is considered as a possibility.",
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T1 - Proton-transferring systems studied by vibrational spectroscopy and theoretical ab initio calculations. The S0 and T1 states of [2,2′-bipyridine]-3,3′-diol

AU - Mordzinski, A.

AU - Kownacki, K.

AU - Les, A.

AU - Oyler, N. A.

AU - Adamowicz, Ludwik

AU - Langkilde, F. W.

AU - Wilbrandt, R.

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N2 - Tautomerization and phototautomerization of [2,2′-bipyridine]-3,3′-diol is investigated by means of infrared, Raman, and time-resolved resonance Raman spectroscopies and ab initio theoretical calculations. Full ab initio SCF (self-consistent field method) geometry optimization followed by MBPT (2)/6-31G** (second-order many-body perturbation theory) energy calculations of both tautomeric forms in the ground state and the lowest excited triplet state is reported and discussed. Two tautomeric forms. A (dihydroxy) and B (dioxo) are found to be minima on the S0 and T1 potential energy surfaces. While form A is the most stable one in the ground state, the energetic ordering is reversed when going to the triplet state. A good agreement between the experimental and calculated vibrational spectra allows a reliable assignment of most vibrational bands corresponding to tautomer A in the ground state. To assign the observed triplet-triplet optical transition and estimate intensities of resonance Raman bands in the triplet state, excitation energies and oscillator strengths of higher triplet states relative to T1 are calculated. Tentative assignments for the resonance Raman bands observed in the lowest excited triplet state are given. All observed vibrational bands are assigned to totally symmetric modes of the most stable B form. From a comparison of the observed and calculated T1 resonance Raman spectra, it is concluded that two transitions, namely, T1 → T5 and T1 → T8, contribute to the resonance Raman scattering and to the triplet-triplet absorption band observed around 430 nm. These states are both of Ag symmetry and are calculated at 3.15 (T5) and 4.80 eV (T8) above T1 (Bu). In view of the fact that the exciting wavelength (around 430 nm, 2.88 eV) is substantially out of resonance with the calculated T1 → T8 transition, vibronic coupling between T5 and T8 is considered as a possibility.

AB - Tautomerization and phototautomerization of [2,2′-bipyridine]-3,3′-diol is investigated by means of infrared, Raman, and time-resolved resonance Raman spectroscopies and ab initio theoretical calculations. Full ab initio SCF (self-consistent field method) geometry optimization followed by MBPT (2)/6-31G** (second-order many-body perturbation theory) energy calculations of both tautomeric forms in the ground state and the lowest excited triplet state is reported and discussed. Two tautomeric forms. A (dihydroxy) and B (dioxo) are found to be minima on the S0 and T1 potential energy surfaces. While form A is the most stable one in the ground state, the energetic ordering is reversed when going to the triplet state. A good agreement between the experimental and calculated vibrational spectra allows a reliable assignment of most vibrational bands corresponding to tautomer A in the ground state. To assign the observed triplet-triplet optical transition and estimate intensities of resonance Raman bands in the triplet state, excitation energies and oscillator strengths of higher triplet states relative to T1 are calculated. Tentative assignments for the resonance Raman bands observed in the lowest excited triplet state are given. All observed vibrational bands are assigned to totally symmetric modes of the most stable B form. From a comparison of the observed and calculated T1 resonance Raman spectra, it is concluded that two transitions, namely, T1 → T5 and T1 → T8, contribute to the resonance Raman scattering and to the triplet-triplet absorption band observed around 430 nm. These states are both of Ag symmetry and are calculated at 3.15 (T5) and 4.80 eV (T8) above T1 (Bu). In view of the fact that the exciting wavelength (around 430 nm, 2.88 eV) is substantially out of resonance with the calculated T1 → T8 transition, vibronic coupling between T5 and T8 is considered as a possibility.

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