Theoretical characterization of the potential energy curve for hydrogen atom addition to molecular oxygen

Journal Article · Sun Mar 15 04:00:00 EST 1981 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.441501· OSTI ID:6790656

Dunning, Jr, T H; Walch, S P; Goodgame, M M

Large scale polarization configuration interaction (POL-CI) calculations are reported on the HO/sub 2/ molecule. For the structure of the stable complex the calculations predict (with experimental values in parentheses) R/sub OH/=0.99 A(0.971 A), R/sub OO/=1.37 A (1.335 A), and theta/sub HOO/=103/sup 0/(104.1/sup 0/). The calculated harmonic frequencies (3655, 1416, and 1181 cm/sup -1/) are also in good agreement with those derived from experiment. On the other hand, the H--O/sub 2/ bond energy obtained in the calculations (42 kcal/mole) is too small by approx.10 kcal/mole (an inherent defect in the POL-CI method). Although both the GVB and GVB-CI calculations predict barriers of approx.3 kcal/mole to the addition of a hydrogen atom to molecular oxygen, the POL-CI calculations reduce the barrier to less than 0.4 kcal/mole. Taking the computational limitations into account, there may well be no barrier at all to the addition reaction.

• Research Organization: Theoretical Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439
• OSTI ID: 6790656
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 74:6; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CHALCOGENIDES
CHEMICAL REACTIONS
COMBUSTION
CONFIGURATION INTERACTION
ELEMENTS
ENERGY
HYDROGEN
HYDROGEN COMPOUNDS
MOLECULAR STRUCTURE
NONMETALS
OXIDATION
OXIDES
OXYGEN
OXYGEN COMPOUNDS
POTENTIAL ENERGY
THERMOCHEMICAL PROCESSES