title: Mechanically induced generation of highly reactive excited-state oxygen molecules in cluster scattering.
abstract: Molecular electronic excitation in (O(2))(n) clusters induced by mechanical collisions via the "chemistry with a hammer" is investigated by a combination of molecular dynamics simulations and quantum chemistry calculations. Complete active space self-consistent field augmented with triple-zeta polarizable basis set quantum chemistry calculations of a compressed (O(2))(2) cluster model in various configurations reveal the emergence of possible pathways for the generation of electronically excited singlet O(2) molecules upon cluster compression and vibrational excitation, due to electronic curve-crossing and spin-orbit coupling. Extrapolation of the model (O(2))(2) results to larger clusters suggests a dramatic increase in the population of electronically excited O(2) products, and may account for the recently observed cluster-catalyzed oxidation of silicon surfaces, via singlet oxygen generation induced by cluster impact, followed by surface reaction of highly reactive singlet O(2) molecules. Extensive molecular dynamics simulations of (O(2))(n) clusters colliding onto a hot surface indeed reveal that cluster compression is sufficient under typical experimental conditions for nonadiabatic transitions to occur. This work highlights the importance of nonadiabatic effects in the "chemistry with a hammer."
authors.affiliation: Centre for Research in Molecular Modeling and Department of Chemistry & Biochemistry, Concordia University, Montréal, Québec, H4B 1R6, Canada.
authors.forename: Tao-Nhân V
authors.initials: TN
authors.lastname: Nguyen
authors.forename: Qadir K
authors.initials: QK
authors.lastname: Timerghazin
authors.forename: Holger
authors.initials: H
authors.lastname: Vach
authors.forename: Gilles H
authors.initials: GH
authors.lastname: Peslherbe
mesh_terms: D002384:Catalysis; D056004:Molecular Dynamics Simulation; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D012825:Silicon / Q000737:chemistry; D013499:Surface Properties; D014732:Vibration
chemical_list: D010100:Oxygen; D012825:Silicon