Reactions of Nb₂ and Nb₃ with CO, D₂, N₂, and O₂: Reconciling experimental kinetics with density functional theory-calculated reaction profiles

Abstract

Calculated energy profiles for the reactions of neutral Nb(2) and Nb(3) metal clusters with CO, D(2), N(2), and O(2) are presented. In each reaction path, both a physisorption energy minimum, where the reactant remains intact, and a chemisorption energy minimum, where the reactant has dissociated, are calculated and linked by saddle points. We calculate branching ratios for the forward (dissociative) and reverse reactions which we compare with the experimental kinetic data. It is found that a combination of average thermal energies and barrier heights leads to wide variation in branching ratios which compares favourably to previously determined experimental reaction rates.