Quantum mechanical mechanisms of inelastic and reactive H + D(2)(v = 0, j = 2) collisions.
This article analyses the mechanisms of inelastic and reactive H + D(2)(v = 0, j = 2) collisions that result in highly vibrationally excited products when the collision energy is 1.70 eV. The analytical method is entirely quantum mechanical and focuses on correlations between the polarization of the reactant molecule and the direction of product scattering. Two viewpoints are used. The "intrinsic" viewpoint reveals the reactant polarizations that lead to the largest cross section at each value of the scattering angle (the angle between the reactant-approach and product-recoil directions); the "extrinsic" viewpoint reveals how the dependence of the collision cross section on the scattering angle changes when the reactant polarization is fixed at each one of a set of experimentally feasible alternatives. Comparison of processes correlating with the same range of impact parameters is also used, to facilitate isolation and identification of directional effects. When products are scattered in the backward and sideways regions, the results for inelastic and reactive collisions are rather similar. When products are scattered in the forward region, the results for inelastic and reactive collisions are clearly different: a side-on collision geometry that largely increases the inelastic cross section hardly affects the reactive cross section. This feature is the quantum mechanical signature of the so-called "tug-of-war" mechanism.
Aldegunde
Jesús
J
Grupo de Dinámica Molecular, Departamento de Química Física, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008 Salamanca, Spain. jalde@usal.es
Jambrina
P G
PG
Sáez-Rábanos
Vicente
V
de Miranda
Marcelo P
MP
Aoiz
F J
FJ
D003903:Deuterium / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics; D014732:Vibration
D006859:Hydrogen; D003903:Deuterium