The Journal of Chemical Physics · 1976 · 99 citations · 32 references
Natural SciencesChemistryPhysicsComputational ChemistryQuantum ChemistryTheoretical ChemistryAb Initio MethodsMolecular Orbital TheoryMolecular VibrationPotential Energy SurfacesReaction DynamicsReaction MechanismsAttractive Force ModelsMolecular Potential Energy SurfacesMolecular Vibrational DynamicsPotential Energy Surface ConstructionPromoting VibrationsReactive Potential Energy SurfacesSurface PotentialVibrationally Excited Reaction Pathways
Total cross sections for the reaction of H+2(v′) with He were calculated for v′=0 to 5 over a range of total energies between 1 and 5 eV using classical mechanics. The potential surface used was an appropriate diatomics-in-molecules function adjusted to fit existing ab initio points. In agreement with experiment, reagent vibrational excitation is very effective in promoting formation of HeH+ or dissociation, a fact which we explain in terms of the increased range of the attractive forces when the H+2 bond is extended. This effect is not properly described by comparison collinear calculations.
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