Theoretical study of the potential energy surface for O(/sup 3/P)+H/sub 2/

Journal Article · Tue Jan 01 04:00:00 EST 1980 · J. Chem. Phys.; (United States)

OSTI ID:5773587

Walch, S P; Dunning, Jr, T H; Raffenetti, R C; Bobrowicz, F W

Barrier heights and transition state geometries have been calculated for the reaction O(/sup 3/P)+H/sub 2/..-->..OH+H using large scale POL-CI wave functions (based on GVB wave functions using basis sets of up to triple zeta valence plus double zeta polarization quality). A detailed study was made of the effects on the calculated barrier height and saddle point geometry of (i) basis set, (ii) choice of orbitals, and (iii) choice of reference configurations. Calculations using a (4s3p2d/3s2p) basis lead to a collinear saddle point with r/sub HH/=0.92 A and r/sub OH/=1.23 A with a corresponding barrier height of 12.5 kcal/mole. There are two surfaces which connect the reactants with the products: one of /sup 3/A' symmetry and one of /sup 3/A'' symmetry (these correspond to the two degenerate components of the /sup 3/Pi state in collinear geometries). In the transition state region, the /sup 3/A' surface has a steeper bending curve than the /sup 3/A'' surface leading to significantly different reaction rates on the two surfaces.

• Research Organization: Theoretical Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne,Illinois 60439
• OSTI ID: 5773587
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 72:1; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
COMBUSTION
CRYOGENIC FLUIDS
ELEMENTS
ENERGY
FLUIDS
HYDROGEN
NONMETALS
OXIDATION
OXYGEN
POTENTIAL ENERGY
THERMOCHEMICAL PROCESSES