title: Calculated vibrational states of ozone up to dissociation.
abstract: A new accurate global potential energy surface for the ground electronic state of ozone [R. Dawes et al., J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. Here we present global "three-well" calculations of all bound vibrational states of three isotopic combinations of ozone ((48)O3, (16)O2 (18)O, (16)O2 (17)O) for J = 0 and J = 1 with a focus on the character and density of highly excited states and discuss their impact on the ozone isotopic anomaly. The calculations were done using a parallel symmetry-adapted Lanczos method with the RV3 code. Some comparisons were made with results obtained with the improved relaxation method implemented in the Heidelberg multi-configuration time-dependent Hartree code.
authors.affiliation: Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409, USA.
authors.forename: Steve
authors.initials: S
authors.lastname: Ndengué
authors.affiliation: Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409, USA.
authors.forename: Richard
authors.initials: R
authors.lastname: Dawes
authors.affiliation: Chemistry Department, Queen's University, Kingston, Ontario K7L 3N6, Canada.
authors.forename: Xiao-Gang
authors.initials: XG
authors.lastname: Wang
authors.affiliation: Chemistry Department, Queen's University, Kingston, Ontario K7L 3N6, Canada.
authors.forename: Tucker
authors.initials: T
authors.lastname: Carrington
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China and Center for Advanced Chemical Physics and 2011 Frontier Center for Quantum Science and Technology, University of Science and Technology of China, 96 Jinzhai Road, Hefei 230026, China.
authors.forename: Zhigang
authors.initials: Z
authors.lastname: Sun
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
authors.forename: Hua
authors.initials: H
authors.lastname: Guo