QUANTUM-MECHANICAL RATE CONSTANTS FOR O-REVERSIBLE-ARROW-H+O-2 FOR TOTAL ANGULAR-MOMENTUM J-GREATER-THAN-0(OH)

Thermal rate constants have been calculated for the titled reaction fo r total angular momentum J > 0 using the quantum flux correlation func tion methodology of Thompson and Miller [Thompson, W. H.; Miller, W. H . J. Chem. Phys. 1995, 102, 7409]. This generalizes earlier work by tw o of us [Germann,T. C.; Miller, W. H. J. Phys. Chem. A 1997, 101, 6358 ] for J = 0. A helicity conserving approximation (HCA) is used for the present J > 0 calculations, and it and other approximations for treat ing J > 0 are discussed and compared. The results show that for this r eaction the much simpler J-shifting approximation (JSA) is reasonably accurate (to 10-20% in the rate constants), provided the appropriate c hoice is made for the reference geometry in this approach.