The nature of bonding in metal-metal singly bonded coinage metal dimers: Cu₂ , Ag₂ and Au₂

Slavko Radenković (1, 2) , David Danovich (3) , Sason Shaik (3) , Philippe C. Hiberty (4) , Benoît Braïda (1)

1 LCT - Laboratoire de chimie théorique
2 University of Kragujevac
3 HUJ - The Hebrew University of Jerusalem
4 LCPO - Laboratoire de Chimie Physique D'Orsay

The nature of the single bond in the three isoelectronic coinage metal dimers Cu2, Ag2 and Au2 is investigated by means of the ab initio Breathing Orbital Valence Bond (BOVB) method, which allows one to calculate the respective contributions of the covalent and ionic structures to the total wave function, as well as the resonance energy arising from their mixing. It is shown that the BOVB method at its highest level provides bond dissociation energies in very good agreement with reference CCSD(T) values for the three dimers. It is also found that the covalent/ionic resonance energy is important in all three cases, contributing to 40-50% to the total bonding energy, thus qualifying the bonds in Cu2 and Au2 as quasi-charge-shift bonds, and that of Ag2 as a borderline case in-between classical covalent bond and charge-shift one. These results are further confirmed by analyses of the wave functions in terms of the Atoms-in-Molecule theory, which show that the Laplacian of the density at the bond critical point is large and positive in all three cases, which classifies the three bonds as charge-shift bonds within this theory.

Mots clés: Valence-Bond Theory; Hybridization; Non-Orthogonal Orbitals; Chemical bond; Charge Shift Bond; metal bonding

Domaines: Chimie théorique et/ou physique

Slavko Radenković, David Danovich, Sason Shaik, Philippe C. Hiberty, Benoît Braïda. The nature of bonding in metal-metal singly bonded coinage metal dimers: Cu₂ , Ag₂ and Au₂. Journal of Theoretical and Computational Chemistry, 2017, 1116, pp.195-201. ⟨10.1016/j.comptc.2017.02.013⟩. ⟨hal-01514930⟩