K. Moribayashi et H. Nakamura, ACCURATE QUANTUM DYNAMICS OF THE LIGHT ATOM-TRANSFER CHEMICAL-REACTION O-]OH+CL(HCL), Journal of physical chemistry, 99(42), 1995, pp. 15410-15420
The hydrogen atom transfer reaction between two heavy atoms, upsilon(i
)=0j(i)=0-2)-->OH(upsilon(f)=0,1j(f))+Cl, is studied quantum mechanica
lly accurately with use of the hyperspherical coordinate approach, whe
re upsilon(lambda) and j(lambda) designate the vibrational and rotatio
nal quantum numbers in the lambda arrangement channel. The collision e
nergy considered in this study ranges up to similar to 0.7 eV, and the
total angular momentum J is required up to similar to 120. The potent
ial energy surface employed is the one derived by Koizumi, Schatz, and
Gordon (KSG) based on ab initio data. The effects of the potential en
ergy surface topography on the dynamics are analyzed in terms of the c
ollision energy dependence and the j(i) dependence. The effects of the
nonlinearity of the transition state of the KSG surface is clearly ma
nifested in these dynamics. Not only the accurate integral cross secti
on and the rate constant are evaluated, but also the Omega(i) dependen
ce of the dynamics and final rotational state distribution are analyze
d, where Omega(i) is the z-component of J in the initial arrangement c
hannel. The j(f) distribution at E(coll)greater than or equal to 0.5 e
V shows an interesting resemblance with the feature recently observed
experimentally. The energy-shift approximation is extended so as to co
ver the general triatomic systems which require a large number of J. T
his extended CCPA (constant centrifugal potential approximation) is sh
own to work well.