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

Comments

Originally published at http://doi.org/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

Included in

Physics Commons

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