Theoretical study of the potential energy surface for OH+H/sub 2/

Journal Article · Tue Jan 15 04:00:00 EST 1980 · J. Chem. Phys.; (United States)

OSTI ID:5550133

Walch, S P; Dunning, Jr, T H

Barrier heights and transition state geometries have been calculated for the reaction OH+H/sub 2/..-->..H/sub 2/O+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). The saddle point geometry is found to be coplanar and to resemble OH+H/sub 2/ as expected because of the large exoergicity (approx.16 kcal/mole) of the reaction. The OH distance of the OH moiety is essentially the same as for the OH molecule, while the HH distance of the H/sub 2/ moiety is 0.10 A (approx.14%) longer than for H/sub 2/. The distance from the O to the near hydrogen of the H/sub 2/ moiety is 0.35 A (approx.36%) longer than for the H/sub 2/O molecule. The HOH angle is 98/sup 0/ and the H/sub 2/ moiety is tilted from collinearity with the O atom by 15/sup 0/ toward the H of the OH moiety. The calculated barrier height using a (4s3p2d/3s2p) basis set is 6.2 kcal/mole. Transition state theory calculations (including a Wigner tunneling correction) using the theoretically computed surface predict rate constants which are in excellent agreement with experiment over the temperature range of 300--2000 /sup 0/K.

• Research Organization: Theoretical Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 5550133
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 72:2; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CRYOGENIC FLUIDS
ELEMENTS
ENERGY
FLUIDS
HIGH TEMPERATURE
HYDROGEN
HYDROXYL RADICALS
KINETICS
MEDIUM TEMPERATURE
NONMETALS
POTENTIAL ENERGY
RADICALS
REACTION KINETICS
VERY HIGH TEMPERATURE