Title

Theoretical Characterization of the Potential Energy Surface for H + O2 HO2* OH + O. III. Computed Points to Define a Global Potential Energy Surface

Author(s)

S P. Walch

Document Type

Article

Publication Date

1991

Publication Source

Journal of Chemical Physics

Volume

94

Inclusive pages

7068

Peer Reviewed

yes

Abstract

Recent a b i n i t i o calculations have focused on the minimum energy path region of this surface [J. Chem. Phys. 8 8, 6273 (1988), Paper I] and on the saddle point region for H atom exchange via a T‐shaped HO2 complex (J. Chem. Phys. 9 1, 2373 (1989), Paper II). In this paper, the results of additional calculations are discussed that, combined with the previously reported results, provide a global representation of the potential energy surface for this reaction. Complete active space SCF/externally contracted configuration interaction calculations (CASSCF/CCI) were carried out using the same wave function employed in II. The new calculations presented here characterize the potential energy surface for a variety of H atom approach angles, ranging from perpendicular to collinear (measured with respect to the O2bond) and for a variety of H atom to O2 center‐of‐mass distances. Additionally, a new collinear exchange saddle point is reported. Using the a b i n i t i o results from these new calculations, optimal geometries, and harmonic frequencies based on local polynomial representations of the potential energy surface are reported along the constrained energy minimum path, while anharmonic frequencies are calculated at both the O2 and OH asymptotes and at the HO2 intermediate.

Disciplines

Chemistry

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