title: F + (H2O)2 reaction: the second water removes the barrier.
abstract: In light of controversy concerning the classical barrier for the F + H2O → HF + OH reaction, higher level theoretical methods are applied. Both aug-cc-pV5Z CCSD(T) and cc-pVQZ full CCSDT methods predict a low classical barrier of about 2 kcal/mol. For the analogous water dimer reaction, the presence of the second water molecule erases this barrier entirely. An entrance complex F···(H2O)2 is found lying 7.3 kcal/mol below separated F + (H2O)2. A barrier follows this complex on the reaction coordinate, but lying 3.1 kcal/mol below the reactants. There is also an exit complex HF···H2O3 lying 11.0 kcal/mol below the separated products HF + H2O3. Thus the reactions of atomic fluorine with the water monomer and dimer are qualitatively different.
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: Guoliang
authors.initials: G
authors.lastname: Li
authors.forename: Qian-Shu
authors.initials: QS
authors.lastname: Li
authors.forename: Yaoming
authors.initials: Y
authors.lastname: Xie
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer