Potential energy surface and quantum dynamics study of rovibrational states for HO3 (X 2A″)?

Physical Chemistry Chemical Physics Pub Date: 2008-04-08 DOI: 10.1039/B801928B

Abstract

An analytic potential energy surface has been constructed by fitting to about 28 thousand energy points for the electronic ground-state (X?2A″) of HO3. The energy points are calculated using a hybrid density functional HCTH and a large basis set aug-cc-pVTZ, i.e., a HCTH/aug-cc-pVTZ density functional theory (DFT) method. The DFT calculations show that the trans-HO3 isomer is the global minimum with a potential well depth of 9.94 kcal mol?1 with respect to the OH + O2 asymptote. The equilibrium geometry of the cis-HO3 conformer is located 1.08 kcal mol?1 above that of the trans-HO3 one with an isomerization barrier of 2.41 kcal mol?1 from trans- to cis-HO3. By using this surface, a rigorous quantum dynamics (QD) study has been carried out for computing the rovibrational energy levels of HO3. The calculated results determine a dissociation energy of 6.15 kcal mol?1, which is in excellent agreement with the experimental value of Lesteret al. [J. Phys. Chem. A, 2007, 111, 4727.]

Graphical abstract: Potential energy surface and quantum dynamics study of rovibrational states for HO3 (X?2A″)
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