K. Nobusada et al., QUANTUM DYNAMICS OF O(P-3)-]OH+CL - EFFECTS OF REAGENT ROTATIONAL-EXCITATION(HCL), Journal of the Chemical Society. Faraday transactions, 93(5), 1997, pp. 721-726
Citations number
34
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
Accurate quantum dynamics of the chemical reaction O(P-3) + HCl(j(i),
v(i) = 0) --> CH(j(f), v(f) = 0) + Cl is studied using the hyperspheri
cal coordinate approach and the Koizumi-Schatz-Gordon (KSG) potential-
energy surface. The effects of reagent rotational excitation on the dy
namics are investigated. The study considers total energies up to 0.7
eV and reagent rotational states, j(i) = 0-10. The total reaction cros
s-section shows a strong dependence on j(i). Initially it decreases wi
th increasing j(i), up to j(i) approximate to 4, and then increases wi
th further increase in j(i). This overall trend is enhanced on increas
ing the total energy. The final rotational state (j(f)) distributions
are also investigated. Interestingly, the distribution shows a peak at
high j(f) (approximate to 10) irrespective ofj(i) and the total energ
y. The qualitative features are quite similar to the experimental resu
lts. Finally, the state-resolved rate constant and the thermal rate co
nstant are evaluated. Because of the enhancement of the reaction by th
e reagent rotational excitation, the state-resolved rate constants for
8 less than or similar to j(i) less than or equal to 10 are two or th
ree orders of magnitude larger than those for j(i) less than or simila
r to 5. The thermal rate constant obtained is thus much larger than th
e experimental data implying that the barrier height of the KSG surfac
e may be too low.