title: Ferromagnetic bonding: high spin copper clusters (n+1)Cu(n); n = 2-14) devoid of electron pairs but possessing strong bonding.
abstract: Density functional theoretic studies are performed for the high-spin copper clusters (n)(+1)Cu(n) (n = 2-14), which are devoid of electron pairs shared between atoms, hence no-pair clusters (J. Phys. Chem. 1988, 92, 1352; Isr. J. Chem. 1993, 33, 455; J. Am. Chem. Soc. 1999, 121, 3165). Despite the lack of electron pairing, it is found that the bond dissociation energy per atom (BDE/n) is significant and converges (to within 1 kcal mol(-1)), around a cluster size (11)Cu(10), to a value of BDE/n = 19 kcal mol(-1). This is a very large bonding energy, much larger than has previously been obtained for no-pair clusters of lithium, BDE/n = 12 kcal mol(-1), or sodium clusters, BDE/n = 3 kcal mol(-1). This bonding, so-called ferromagnetic bonding (FM-bonding) is analyzed using a valence bond (VB) model (J. Phys. Chem. A 2002, 106, 4961; Phys. Chem. Chem. Phys. 2003, 5, 158). As such, FM-bonding in no-pair clusters is described as an ionic fluctuation, of the triplet pair, that spreads over all the close neighbors of a given atom in the clusters. Thus, if we refer to each triplet pair and its ionic fluctuations as a local FM-bond, we can regard the electronic structure of a given (n)(+1)M(n) cluster as a resonance hybrid of all the local FM-bonds between close neighbors. The model shows how a weak interaction in the diatomic triplet molecule can become a remarkably strong binding force that binds together mono-valent atoms without even a single electron pair. This is achieved because the growing number of VB structures exerts a cumulative effect of stabilization that is maximized when the cluster has a compact structure with an optimal coordination number for the atoms.
authors.affiliation: The Manchester Interdisciplinary Biocenter, School of Chemical Engineering and Analytical Science, The University of Manchester, Sackville Street, PO Box 88, Manchester M60 1QD, UK.
authors.forename: Sam P
authors.initials: SP
authors.lastname: de Visser
authors.forename: Devesh
authors.initials: D
authors.lastname: Kumar
authors.forename: Mark
authors.initials: M
authors.lastname: Danovich
authors.forename: Nir
authors.initials: N
authors.lastname: Nevo
authors.forename: David
authors.initials: D
authors.lastname: Danovich
authors.forename: Pankaz K
authors.initials: PK
authors.lastname: Sharma
authors.forename: Wei
authors.initials: W
authors.lastname: Wu
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik
mesh_terms: D001565:Benzoates; D003300:Copper / Q000737:chemistry*; D004583:Electrons; D008956:Models, Chemical; D008968:Molecular Conformation; D009769:Object Attachment; D010084:Oxidation-Reduction; D013816:Thermodynamics
chemical_list: D001565:Benzoates; C058271:4-(2-(4-isopropylbenzamido)ethoxy)benzoic acid; D003300:Copper