On the Nature of Bonding in Parallel Spins in Monovalent Metal Clusters

David Danovich; Sason Shaik

doi:10.1146/annurev-physchem-040215-112324

Annual Review of Physical Chemistry

Volume 67, 2016

Review Article

Free

On the Nature of Bonding in Parallel Spins in Monovalent Metal Clusters

David Danovich¹, and Sason Shaik¹
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Affiliations: Institute of Chemistry, The Hebrew University, 91904 Jerusalem, Israel; email: [email protected], [email protected] Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University, 91904 Jerusalem, Israel
Vol. 67:419-439 (Volume publication date May 2016) https://doi.org/10.1146/annurev-physchem-040215-112324
First published as a Review in Advance on April 08, 2016
© Annual Reviews

Abstract

As we approach the Lewis model centennial, it may be timely to discuss novel bonding motifs. Accordingly, this review discusses no-pair ferromagnetic (NPFM) bonds that hold together monovalent metallic atoms using exclusively parallel spins. Thus, without any traditional electron-pair bonds, the bonding energy per atom in these clusters can reach 20 kcal mol⁻¹. This review describes the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that are delocalized over all the close neighbors of a given atom in the cluster. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry and for the very steep rise of the bonding energy per atom. The advent of NPFM clusters offers new horizons in chemistry of highly magnetic species sensitive to magnetic and electric fields.

Keyword(s): alkali metal clusters, bound triplet pairs, coinage metal clusters, no-pair ferromagnetic bonding, valence bond theory

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