Ab initio MRD-CI Study of the Electronic Spectrum of Tribromomethanol Br3COH and the Photofragmentation along Br–C and C–O Cleavage
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M. Mühlhäuser
Abstract
Multi reference configuration interaction calculations are carried out to compute the electronic spectrum of tribromomethanol Br3COH. The first dipole-allowed transitions are computed at 5.0 eV (11A″ ← X1A′) and 5.4 eV (21A″ ← X1A′) followed by three transitions at 5.5 eV (21A′ ← X1A′) and 6.1 eV (31A′ ← X1A′, 31A″ ← X1A′). The largest oscillator strength (f = 0.08) is obtained for the σ → σ* type excitation 31A″ ← X1A′ computed around 6.1 eV. The corresponding triplet states are also given. Five low-lying excited states in the energy range between 4.5 eV and 5.5 eV are found to be highly repulsive for Br–C elongation, leading to Br2CHOH (X2A′) and Br (X2P), so that tribromomethanol Br3COH is expected to be important for atmospheric chemistry as reservoir of Br radicals. Photodissociation along C–O cleavage resulting in Br3C (X2A′) and OH (X2Π) has to overcome a barrier of about 0.7 eV because the low-lying excited states 11A″, 13A′ and 13A″ become repulsive only after elongating the C–O bond by about 0.45 Å.
© 2003 Oldenbourg Wissenschaftsverlag GmbH
Articles in the same Issue
- The Characterization of Metal–Metal Bonds in Unsaturated Binuclear Homoleptic Transition Metal Carbonyls. The Compliance Matrix
- Quantum Chemical Investigation of Spin-Forbidden Transitions in Dithiosuccinimide
- Rovibronic States in the X2Π State of the CCS− Anion
- Ab initio MRD-CI Study of the Electronic Spectrum of Tribromomethanol Br3COH and the Photofragmentation along Br–C and C–O Cleavage
- Theoretical Study of the Dissociation and Isomerization of NCS
- Theoretical Study of the Vertical Electronic Spectra, Electron-Spin g-Factors and Hyperfine Coupling Constants of the (C2v) Cyclic Radicals C3+, Si3+, C3− and Si3−
- Measurement of the 129Xe NMR Chemical Shift of Supercritical Xenon
Articles in the same Issue
- The Characterization of Metal–Metal Bonds in Unsaturated Binuclear Homoleptic Transition Metal Carbonyls. The Compliance Matrix
- Quantum Chemical Investigation of Spin-Forbidden Transitions in Dithiosuccinimide
- Rovibronic States in the X2Π State of the CCS− Anion
- Ab initio MRD-CI Study of the Electronic Spectrum of Tribromomethanol Br3COH and the Photofragmentation along Br–C and C–O Cleavage
- Theoretical Study of the Dissociation and Isomerization of NCS
- Theoretical Study of the Vertical Electronic Spectra, Electron-Spin g-Factors and Hyperfine Coupling Constants of the (C2v) Cyclic Radicals C3+, Si3+, C3− and Si3−
- Measurement of the 129Xe NMR Chemical Shift of Supercritical Xenon
