A quantum dynamics study of D{sub 2}+OH{r-arrow}DOH+D on the WSLFH potential energy function

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 107; no. 37 ; Sep. 18, 2003
• Main Authors: Defazio, P., Gray, S. K., Chemistry, Univ. di Siena
• Format: Journal Article
• Language: English
• Published: United States 18-09-2003
• Subjects: ANGULAR MOMENTUM; CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; CROSS SECTIONS; DYNAMICS; FUNCTIONS; IMPLEMENTATION; POTENTIAL ENERGY; TUNNEL EFFECT; WAVE PACKETS
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp030190a

The quantum dynamics of the reaction D{sub 2} + OH {yields} DOH + D on the Wu-Schatz-Lendvay-Fang-Harding ab initio-based potential energy function is investigated. A recently developed four-atom implementation of the real wave packet method is employed. Extensive six-dimensional calculations for a total angular momentum of J = 0 and, within the helicity-decoupled approximation, numerous J > 0 calculations are performed. Cross sections and rate constants for reaction are estimated using a J-shifting procedure and compared with quasi-classical trajectory, transition state theory, and experimental results. The results are also contrasted with comparable results for H{sub 2} + OH. A surprising feature is that our rate constants agree best with zero-curvature transition state theory results, indicating that tunneling may not be as important as expected.