title: Anharmonic Rice-Ramsperger-Kassel-Marcus (RRKM) and product branching ratio calculations for the partially deuterated protonated water dimers: dissociation and isomerization.
abstract: Partially deuterated protonated water dimers, H2O·H(+)·D2O, H2O·D(+)·HDO, and HDO·H(+)·HDO, as important intermediates of isotopic labeled reaction of H3O(+) + D2O, undergo direct dissociation and indirect dissociation, i.e., isomerization before the dissociation. With Rice-Ramsperger-Kassel-Marcus theory and ab initio calculations, we have computed their dissociation and isomerization rate constants separately under the harmonic and anharmonic oscillator models. On the basis of the dissociation and isomerization rate constants, branching ratios of two primary products, [HD2O(+)]∕[H2DO(+)], are predicted under various kinetics models with the harmonic or anharmonic approximation included. The feasible kinetics model accounting for experimental results is shown to include anharmonic effect in describing dissociation, while adopting harmonic approximation for isomerization. Thus, the anharmonic effect is found to play important roles affecting the dissociation reaction, while isomerization rates are shown to be insensitive to whether the anharmonic or harmonic oscillator model is being applied.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China.
authors.forename: Di
authors.initials: D
authors.lastname: Song
authors.forename: Hongmei
authors.initials: H
authors.lastname: Su
authors.forename: Fan-ao
authors.initials: FA
authors.lastname: Kong
authors.forename: Sheng-Hsien
authors.initials: SH
authors.lastname: Lin
mesh_terms: D003198:Computer Simulation; D003903:Deuterium / Q000737:chemistry*; D019281:Dimerization; D007536:Isomerism; D008958:Models, Molecular; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D003903:Deuterium