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), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:20; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
Similar Records
Laser induced fluorescence and resonant two-photon ionization spectroscopy of jet-cooled 1-hydroxy-9,10-anthraquinone
Dipole-bound excess-electron states of adenine tautomers. A theoretical ab initio study
Related Subjects
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
COMPILED DATA
DATA
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
FRANCK-CONDON PRINCIPLE
HETEROCYCLIC COMPOUNDS
INFORMATION
INFRARED SPECTRA
ISOMERIZATION
LASER SPECTROSCOPY
MATHEMATICAL MODELS
MULTIPLETS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PERTURBATION THEORY
PHOTOCHEMICAL REACTIONS
PYRIDINES
RAMAN SPECTROSCOPY
SPECTRA
SPECTROSCOPY
TRIPLETS
VIBRATIONAL STATES