A comparison between reduced dimensionality and mixed quantum/classical evaluations of k(T ) using the flux-flux correlation function formalism

ESTEBAN CLAVERO; JULIANA PALMA

CHEMICAL PHYSICS LETTERS

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2011 vol. 513 p. 139 - 144

0009-2614

Rate constants for the planar H + HD => H2 + D reaction with J=0 have been calculated employing reduced dimensionality, mixed quantum/classical and full quantum computations based on the flux-flux correlation function formalism. It has been found that reduced dimensionality and mixed quantum/classical calculations afford quite similar results. This suggests that, for direct reactions occurring in the gas phase, there is no advantage in using the more involved mixed quantum/classical approach. On the other hand, the comparison between approximate and accurate results indicates that both, reduced dimensionality and mixed quantum/classical approaches, work well at medium and high temperatures. As expected, they fail at very low temperatures where tunnelling prevails.