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

Date

2012-07-16

Authors

Addicoat, Matthew A.
Lim, Kieran F.
Metha, Gregory F.

Journal Title

Journal ISSN

Volume Title

Publisher

American Institute of Physics (AIP)

Abstract

Calculated energy profiles for the reactions of neutral Nb₂ and Nb₃ metal clusters with CO, D₂, N₂, and O₂ 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.

Description

Keywords

Keywords: Barrier heights; Branching ratio; Chemisorption energy; Density functionals; Energy profile; Experimental kinetics; Metal cluster; Physisorption energy; Reaction paths; Reaction profile; Reverse reactions; Saddle point; Chemisorption; Density functional t

Citation

Source

The Journal of Chemical Physics

Type

Journal article

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