Title

Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂

Abstract

The authors report extensive high-level ab initio studies of the first excited (math 2A′) 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(math 1Δg)↔OH+O reaction (J = 0) were studied using an exact wave packet method. The reactions are found to be dominated by sharp resonances.

Department(s)

Chemistry

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2010 American Institute of Physics (AIP), All rights reserved.


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