title: DFT studies of the adsorption and dissociation of H₂O on the Al₁₃ cluster: origins of this reactivity and the mechanism for H₂ release.
abstract: A theoretical study of the chemisorption and dissociation pathways of water on the Al₁₃ cluster was performed using the hybrid density functional B3LYP method with the 6-311+G(d, p) basis set. The activation energies, reaction enthalpies, and Gibbs free energy of activation for the reaction were determined. Calculations revealed that the H₂O molecule is easily adsorbed onto the Al13 surface, forming adlayers. The dissociation of the first H₂O molecule from the bimolecular H₂O structure via the Grotthuss mechanism is the most kinetically favorable among the five potential pathways for O-H bond breaking. The elimination of H₂ in the reaction of an H₂O molecule with a hydrogen atom on the Al cluster via the Eley-Rideal mechanism has a lower activation barrier than the elimination of H₂ in the reaction of two adsorbed H atoms or the reaction of OH and H. Following the adsorption and dissociation of H₂O, the structure of Al₁₃ is distorted to varying degrees.
authors.affiliation: Key Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China.
authors.forename: Jian-Ying
authors.initials: JY
authors.lastname: Zhao
authors.forename: Feng-Qi
authors.initials: FQ
authors.lastname: Zhao
authors.forename: Hong-Xu
authors.initials: HX
authors.lastname: Gao
authors.forename: Xue-Hai
authors.initials: XH
authors.lastname: Ju