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Title: Trajectory surface hopping study of the O({sup 3}P) + C{sub 2}H{sub 2} reaction dynamics: Effect of collision energy on the extent of intersystem crossing

Intersystem crossing (ISC) dynamics plays an important role in determining the product branching in the O({sup 3}P) + C{sub 2}H{sub 2} reaction despite the necessarily small spin-orbit coupling constant values. In this study we investigate the effect of collision energy on the extent of the contribution of a spin non-conserving route through ISC dynamics to the product distributions at the initial collision energies 8.2, 9.5, and 13.1 kcal/mol. A direct dynamics trajectory surface hopping method is employed with potential energy surfaces generated at the unrestricted B3LYP/6-31G(d,p) level of theory to perform nonadiabatic dynamics. To make our calculation simpler, nonadibatic transitions were only considered at the triplet-singlet intersections. At the crossing points, Landau-Zener transition probabilities were calculated using spin-orbit coupling constant values computed at the same geometry. The Landau-Zener model for the title reaction is validated against a more rigorous Tully's fewest switches method and found to be working reasonably well as expected because of weak spin-orbit coupling. We have compared our results with the recent crossed molecular beam experiments and observed a very good agreement with respect to the primary product branching ratios. Our calculation revealed that there is no noticeable effect of the initial collision energy on the overallmore » product distributions that corroborates the recent experimental findings. Our calculation indicates, however, that the extent of intersystem crossing contributions varies significantly with collision energy, needed to be verified, experimentally.« less
Authors:
;  [1]
  1. Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005 (India)
Publication Date:
OSTI Identifier:
22255219
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COLLISIONS; DISTRIBUTION; L-S COUPLING; MOLECULAR BEAMS; POTENTIAL ENERGY; PROBABILITY; SURFACES