The Journal of Chemical Physics · 2012 · 15 citations · 32 references
Natural SciencesChemistryPhysicsComputational ChemistryPhysical ChemistryQuantum ChemistryAb Initio MethodsMolecular CollisionsMolecular Orbital TheoryNonadiabatic DynamicsPotential Energy SurfacesReaction DynamicsAb Initio Potential Energy SurfacesDiabatic Potential Energy SurfacesDiabatic StatesNonadiabatic EffectsNonadiabatic Reaction DynamicsNonadiabatic TransitionsRate ConstantsReactive Potential Energy Surfaces
A set of diabatic potential energy surfaces, that describe the D + DBr → Br(P(1/2,3/2)) + D(2) reaction, is constructed based on MRCI/aug-cc-pV5Z calculations at 29,526 grid points. Time-dependent wave packet calculations are performed for ground-state DBr initially with collision energies up to 2.0 eV to investigate possible electronic nonadiabaticity in this reaction. Reaction probabilities and integral cross sections are calculated. The results show negligible nonadiabatic effects for the title reaction in the energy range considered here, confirming experimental work of Zare and co-workers. In addition, the calculated thermal rate constants are in good agreement with experimental ones.
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