Global potential energy surface, vibrational spectrum, and reaction dynamics of the first excited (Ã (2)A(')) state of HO(2).
The authors report extensive high-level ab initio studies of the first excited (Ã (2)A(')) state of HO(2). 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+O(2)(ã (1)Δ(g))↔OH+O reaction (J=0) were studied using an exact wave packet method. The reactions are found to be dominated by sharp resonances.
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Anyang
A
Li
Daiqian
D
Xie
Richard
R
Dawes
Ahren W
AW
Jasper
Jianyi
J
Ma
Hua
H
Guo