Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂
The authors report extensive high-level ab initio studies of the first excited (Ã A2 ') state of HO2. A global potential energy surface (PES) was developed by spline-fitting 17 000 ab initio points at the internal contracted multireference configuration interaction (icMRCI) level with the AVQZ basis set. To ascertain the spectroscopic accuracy of the PES, the near-equilibrium region of the molecule was also investigated using three interpolating moving least-squares-based PESs employing dynamically weighted icMRCI methods in the complete basis set limit. Vibrational energy levels on all four surfaces agree well with each other and a new assignment of some vibrational features is proposed. In addition, the dynamics of both the forward and reverse directions of the H+ O2 (ã Δ1g) OH+O reaction (J=0) were studied using an exact wave packet method. The reactions are found to be dominated by sharp resonances.
A. Li et al., "Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂," Journal of Chemical Physics, vol. 133, no. 14, American Institute of Physics (AIP), Oct 2010.
The definitive version is available at https://doi.org/10.1063/1.3490642
Keywords and Phrases
Ab initio; Ab initio study; Basis sets; Complete basis set limit; Global potential energy surfaces; Moving least squares; Multi reference configuration interactions; Reaction dynamics; Vibrational energy levels; Vibrational features; Wave-packet method, Potential energy; Potential energy surfaces; Quantum chemistry; Sulfur compounds; Excited states
International Standard Serial Number (ISSN)
Article - Journal
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