Development and application of a ReaxFF reactive force field for oxidative dehydrogenation on vanadium oxide catalysts

We have developed a new ReaxFF reactive force field to describe accurately reactions of hydrocarbons with vanadium oxide catalysts. The ReaxFF force field parameters have been fit to a large quantum mechanics (QM) training set containing over 700 structures and energetics related to bond dissociations, angle and dihedral distortions, and reactions between hydrocarbons and vanadium oxide clusters. In addition, the training set contains charge distributions for small vanadium oxide Clusters and the stabilities of condensed-phase systems. We find that ReaxFF reproduces accurately the QM training set tor structures and energetics of small clusters. Most important is that ReaxFF describes accurately the energetics for various oxidation states of the condensed phases, including V2O5, VO2 and V2O3 in addition to metallic V (V-0). To demonstrate the capability of the ReaxFF force field for describing catalytic processes involving vanadium oxides, we performed molecular dynamics (MD) simulation for reactions of a gas of methanol exposed to the (001) surface of V2O5, We find that formaldehyde is the major product, in agreement with experiment. These studies find that water desorption from surface V-III sites is facilitated by interlayer bonding.