A. Ratkiewicz et al., NONADIABATIC EFFECTS IN THE REACTIONS OF STRONGLY POLAR IONS WITH MOLECULES, Journal of the Chemical Society. Faraday transactions, 92(21), 1996, pp. 4155-4158
Citations number
18
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
A theoretical study has been carried out on the effect of the inclusio
n of the C/r(6) term, where C is a constant and r is the distance betw
een the ion and the centre of mass of the molecule, into the interacti
on potential that describes the capture of an ion by a polar molecule.
Recently, a rotationally adiabatic capture theory was used to show th
at the contribution from such terms alters the rate constants for the
reactions of strongly polar ArH3+ with H2O and NH3 by as much as ca. 2
0%. It is found in this work that non-adiabatic effects resulting from
the coupling of the rotational motion of a dipole with the orbital mo
tion of the system are also of-importance. The magnitude of such effec
ts depends on the molecular parameters of the system