Communication: An Accurate Global Potential Energy Surface for the Ground Electronic State of Ozone
We report a new full-dimensional and global potential energy surface (PES) for the O + O2 → O3 ozone forming reaction based on explicitly correlated multireference configuration interaction (MRCI-F12) data. It extends our previous [R. Dawes, P. Lolur, J. Ma, and H. Guo, J. Chem. Phys. 135, 081102 (2011)] dynamically weighted multistate MRCI calculations of the asymptotic region which showed the widely found submerged reef along the minimum energy path to be the spurious result of an avoided crossing with an excited state. A spin-orbit correction was added and the PES tends asymptotically to the recently developed long-range electrostatic model of Lepers [J. Chem. Phys. 137, 234305 (2012)]. This PES features: (1) excellent equilibrium structural parameters, (2) good agreement with experimental vibrational levels, (3) accurate dissociation energy, and (4) most-notably, a transition region without a spurious reef. The new PES is expected to allow insight into the still unresolved issues surrounding the kinetics, dynamics, and isotope signature of ozone.
R. Dawes et al., "Communication: An Accurate Global Potential Energy Surface for the Ground Electronic State of Ozone," Journal of Chemical Physics, vol. 139, no. 20, American Institute of Physics (AIP), Nov 2013.
The definitive version is available at http://dx.doi.org/10.1063/1.4837175
Keywords and Phrases
Dissociation energies; Electrostatic modeling; Global potential energy surfaces; Ground electronic state; Minimum energy paths; Multi reference configuration interactions; Spin-orbit correction; Structural parameter, Isotopes; Potential energy surfaces; Quantum chemistry; Reefs, Ozone
International Standard Serial Number (ISSN)
Article - Journal
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