title: From gas-phase to liquid-water chemical reactions: the fluorine atom plus water trimer system.
abstract: The potential energy profile for the F+(H2 O)3 →HF+(H2 O)2 OH reaction has been investigated using the "gold standard" CCSD(T) method with correlation-consistent basis sets up to cc-pVQZ. Four different reaction pathways have been found and these are related, both geometrically and energetically. The entrance complexes F⋅⋅⋅(H2 O)3 for all four reaction pathways are found lying ca. 7 kcal mol(-1) below the separated reactants F+(H2 O)3 . The four reaction barriers on their respective reaction coordinates lie ca. 4 kcal mol(-1) below the reactants. There are also corresponding exit complexes HF⋅⋅⋅(H2 O)2 OH, lying about 13 kcal mol(-1) below the separated products HF+(H2 O)2 OH. Compared with analogous F+(H2 O)2 and F+H2 O reactions, the F+(H2 O)3 reaction is somewhat similar to the former but qualitatively different from the latter. It may be reasonable to predict that the reactions between atomic fluorine and water tetramer (or even larger water clusters) may be similar to the F+(H2 O)3 reaction.
authors.affiliation: MOE Key Laboratory of Theoretical Chemistry of the Environment, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510006 (China). glli@scnu.edu.cn, ccq@uga.edu.|Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China). glli@scnu.edu.cn, ccq@uga.edu.|Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602 (USA). glli@scnu.edu.cn, ccq@uga.edu.
authors.forename: Guoliang
authors.initials: G
authors.lastname: Li
authors.affiliation: MOE Key Laboratory of Theoretical Chemistry of the Environment, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510006 (China).
authors.forename: Qian-Shu
authors.initials: QS
authors.lastname: Li
authors.affiliation: Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602 (USA).
authors.forename: Yaoming
authors.initials: Y
authors.lastname: Xie
authors.affiliation: Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602 (USA).
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer
keywords: CCSD(T) theory; atom-molecule reactions; fluorine; potential energy profiles; water trimer