RATE-CONSTANT CALCULATIONS FOR ATOM-DIATOM REACTION INVOLVING AN OPEN-SHELL ATOM AND A MOLECULE IN A SIGMA-ELECTRONIC-STATE - APPLICATION TO THE REACTION AL(P-2(1 X-3-SIGMA(-)(G))-]ALO(X-2-SIGMA(+))+O(P-3(2,1,0))/
D. Reignier et al., RATE-CONSTANT CALCULATIONS FOR ATOM-DIATOM REACTION INVOLVING AN OPEN-SHELL ATOM AND A MOLECULE IN A SIGMA-ELECTRONIC-STATE - APPLICATION TO THE REACTION AL(P-2(1 X-3-SIGMA(-)(G))-]ALO(X-2-SIGMA(+))+O(P-3(2,1,0))/, Journal of the Chemical Society. Faraday transactions (Print), 94(12), 1998, pp. 1681-1686
Citations number
37
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
We present a short study of the influence of the open-shell nature of
the reactants on the kinetics of the title reaction. We use the adiaba
tic capture centrifugal sudden approximation (ACCSA) method and a long
-range potential comprising the sum of the quadrupole-quadrupole, spin
-orbit and dispersion contributions. Matrix elements of this potential
are evaluated in the spinorbit basis set of each reactant for the Al(
P-2(1/2,3/2)) + O-2(X (3)Sigma(g)(-)) reaction and used within the ACC
SA method to calculate the temperature dependence of the rate constant
in the range 15-300 K. In the limit of zero temperature, the reactivi
ties of the two spin-orbit states of the aluminium atom, Al(P-2(1/2))
and Al(P-2(3/2)), towards the O-2 molecule are demonstrated to be diff
erent and analytical formulae for the rate constants are obtained as a
function of temperature.