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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 20, Number 12
BKCSDE 20(12)
December 20, 1999 

Ab Initio Quantum Mechanical Study for the Photolysis and Unimolecular Decomposition Reactions in the Atmosphere of CF3OH
Seung-Joon Kim, Hyun-Sup Song
The electronic transitions from the ground state to low-lying excited states of CF3OH have been investigated using high level ab initio quantum mechanical techniques. Also the possible photodissociation procedures of CF3OH have been considered. The highest level employed in this study is TZP CCSD(T) level of theory. The possible four low-lying excited states can result by the excitation of the lone pair electron (n) in oxygen to σ* molecular orbital in C-O or O-H bond. The vertical transition (n → σ*) energy is predicted to be 220.5 kcal/mol (130 nm) at TZ2P CISD level to theory. The bond dissociation energies of CF3OH to CF3O +H and CF3+OH have been predicted to be 119.5 kcal/mol and 114.1 kcal/mol, respectively, at TZP CCSD level of theory. In addition, the transition state for the unimolecular decomposition of CF3OH into CF2O + HF has been examined. The activation energy and energy separation for this decomposition have been computed to be 43.6kcal/mol and 5.0 kcal/mol including zero-point vibrational energy corrections at TZP CCSD(T) level of theory.
1493 - 1500
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