Quantum approaches for the insertion dynamics of the H{sup +}+D{sub 2} and D{sup +}+H{sub 2} reactive collisions

Journal Article · Tue Nov 15 04:00:00 EST 2005 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2118567· OSTI ID:20723229

Gonzalez-Lezana, Tomas; Aguado, Alfredo; Paniagua, Miguel; Roncero, O ^[1]

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1. Unidad Asociada Universidad Autonoma de Madrid-Consejo Superior de Investigaciones Cientificas (UAM-CSIC), Instituto de Matematicas y Fisica Fundamental, Consejo Superior de Investigaciones Cientificas (CSIC), Serrano 123, Madrid 28006 (Spain)

The H{sup +}+D{sub 2} and D{sup +}+H{sub 2} reactive collisions are studied using a recently proposed adiabatic potential energy surface of spectroscopic accuracy. The dynamics is studied using an exact wave packet method on the adiabatic surface at energies below the curve crossing occurring at {approx_equal}1.5 eV above the threshold. It is found that the reaction is very well described by a statistical quantum method for a zero total angular momentum (J) as compared with the exact ones, while for higher J some discrepancies are found. For J>0 different centrifugal sudden approximations are proposed and compared with the exact and statistical quantum treatments. The usual centrifugal sudden approach fails by considering too high reaction barriers and too low reaction probabilities. A new statistically modified centrifugal sudden approach is considered which corrects these two failures to a rather good extent. It is also found that an adiabatic approximation for the helicities provides results in very good agreement with the statistical method, placing the reaction barrier properly. However, both statistical and adiabatic centrifugal treatments overestimate the reaction probabilities. The reaction cross sections thus obtained with the new approaches are in rather good agreement with the exact results. In spite of these deficiencies, the quantum statistical method is well adapted for describing the insertion dynamics, and it is then used to evaluate the differential cross sections.

• OSTI ID: 20723229
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 123; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
ADIABATIC APPROXIMATION
ANGULAR MOMENTUM
DEUTERIUM IONS
EV RANGE 01-10
HYDROGEN
HYDROGEN IONS 1 PLUS
ION-MOLECULE COLLISIONS
REACTION KINETICS
SUDDEN APPROXIMATION
SURFACES
WAVE PACKETS