Proton-transferring systems studied by vibrational spectroscopy and theoretical ab initio calculations. The S[sub 0] and T[sub 1] states of [2,2[prime]-bipyridine]-3,3[prime]-diol
- Inst. of Physical Chemistry, Warsaw (Poland)
- Univ. of Arizona, Tucson, AZ (United States) Univ. of Warsaw (Poland)
- Univ. of Arizona, Tucson, AZ (United States)
- Risoe National Lab., Roskilde (Denmark)
Tautomerization and phototautomerization of [2,2[prime]-bipyridine]-3,3[prime]-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 S[sub 0] and T[sub 1] 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 T[sub 1] are calculated. Tentative assignments for the resonance Raman bands observed in the lowest excited triplet state are given. 33 refs., 8 figs., 6 tabs.
- DOE Contract Number:
- FG03-93ER61605
- OSTI ID:
- 7019549
- Journal Information:
- Journal of Physical Chemistry; (United States), Vol. 98:20; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
BIPYRIDINES
ELECTRONIC STRUCTURE
INFRARED SPECTRA
ISOMERIZATION
PHOTOCHEMICAL REACTIONS
RAMAN SPECTROSCOPY
VIBRATIONAL STATES
COMPILED DATA
FRANCK-CONDON PRINCIPLE
MATHEMATICAL MODELS
PERTURBATION THEORY
TRIPLETS
AZINES
CHEMICAL REACTIONS
DATA
ENERGY LEVELS
EXCITED STATES
HETEROCYCLIC COMPOUNDS
INFORMATION
LASER SPECTROSCOPY
MULTIPLETS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
SPECTRA
SPECTROSCOPY
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures
990200 - Mathematics & Computers
400500 - Photochemistry