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Open AccessArticle

Electronic Structure of Cubane-Like Vanadium–Nitrogen Cationic Clusters [V4N4]+ and [V6N6]+

1
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
2
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China
3
Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, UK
*
Author to whom correspondence should be addressed.
Inorganics 2019, 7(4), 52; https://doi.org/10.3390/inorganics7040052
Received: 20 March 2019 / Revised: 2 April 2019 / Accepted: 4 April 2019 / Published: 12 April 2019
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
Density Functional Theory and Complete Active Space Self-Consistent Field (CASSCF) methodologies are used to explore the electronic structure of the cationic V–N clusters, [V4N4]+ and [V6N6]+, that have been identified in recent mass spectrometric experiments. Our calculations indicate that both clusters are based on cubane-like fragments of the rock-salt lattice. In the smaller [V4N4]+ cluster, the V–V bonding is delocalized over the tetrahedron, with net bond orders of 1/3 per V–V bond. In [V6N6]+, in contrast, the V–V bonding is strongly localized in the central V2N2 unit, which has a short V=V double bond. CASSCF calculations reveal that both localized and delocalized V–V bonds are highly multi-configurational. View Full-Text
Keywords: clusters; vanadium; density functional theory; CASSCF clusters; vanadium; density functional theory; CASSCF
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MDPI and ACS Style

He, P.; Zhang, J.-G.; McGrady, J.E. Electronic Structure of Cubane-Like Vanadium–Nitrogen Cationic Clusters [V4N4]+ and [V6N6]+. Inorganics 2019, 7, 52.

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