Density Functional Theory Study of Small Vanadium Oxide Clusters

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 111; no. 50; pp. 12938 - 12943
• Main Authors: Jakubikova, Elena, Rappé, Anthony K, Bernstein, Elliot R
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 20-12-2007
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0745844

Density functional theory is employed to study structure and stability of small neutral vanadium oxide clusters in the gas phase. BPW91/LANL2DZ level of theory is used to obtain structures of VO y (y = 1−5), V2O y (y = 2−7), V3O y (y = 4−9), and V4O y (y = 7−12) clusters. Enthalpies of growth and fragmentation reactions of the lowest energy isomers of vanadium oxide molecules are also obtained to study the stability of neutral vanadium oxide species under oxygen saturated gas-phase conditions. Our results suggest that cyclic and cage-like structures are preferred for the lowest energy isomers of neutral vanadium oxide clusters, and oxygen−oxygen bonds are present for oxygen-rich clusters. Clusters with an odd number of vanadium atoms tend to have low spin ground states, while clusters with even number of vanadium atoms have a variety of spin multiplicities for their ground electronic state. VO2, V2O5, V3O7, and V4O10 are predicted to be the most stable neutral clusters under the oxygen saturated conditions. These results are in agreement with and complement previous gas-phase experimental studies of neutral vanadium oxide clusters.