Document Type
Article
Original Publication Date
2017
Journal/Book/Conference Title
JOURNAL OF PHYSICAL CHEMISTRY A
Volume
121
Issue
15
First Page
2990
Last Page
2999
DOI of Original Publication
10.1021/acs.jpca.7b01030
Date of Submission
June 2017
Abstract
The atomic structures, bonding characteristics, spin magnetic moments, and stability of VCUx+, VAgx+, and VAux+ (x = 3-14) clusters were examined using density functional theory. Our studies indicate that the effective valence of vanadium is size-dependent and that at small sizes some of the valence electrons of vanadium are localized on vanadium, while at larger sizes the 3d orbitals of the vanadium participate in metallic bonding eventually quenching the spin magnetic moment. The electronic stability of the clusters may be understood through a split-shell model that partitions the valence electrons in either a delocalized shell or localized on the vanadium atom. A molecular orbital analysis reveals that in planar clusters the delocalizatibn of the 3d orbital of vanadium is enhanced when surrounded by gold due to enhanced 6s-5d hybridization. Once the clusters become three-dimensional, this hybridization is reduced, and copper most readily delocalizes the vanadium's valence electrons. By understanding these unique features, greater insight is offered into the role of a host material's electronic structure in determining the bonding characteristics and stability of localized spin magnetic moments in quantum confined systems.
Rights
Copyright © 2017 American Chemical Society
Is Part Of
VCU Physics Publications
Comments
Originally published at http://doi.org/10.1021/acs.jpca.7b01030