Geometry optimization, energetics, electronic structure, and topology of electron density of dicopper (I) and dichromium (II) tetrakis(μ-acetato)-diaqua complexes are studied focusing on the metal-metal interactions. The performance of broken symmetry (BS) single-determinant ab initio (Hartree-Fock, Møller-Plesset perturbation theory to the second and third orders, coupled clusters singles and doubles) and density functional theory (BLYP, B3LYP, B3LYP-D3, B2PLYP, MPW2PLYP) methods is compared to multideterminant ab initio (CASSCF, NEVPT2) methods as well as to the multipole model of charge density from a single-crystal X-ray diffraction experiment (Herich et al., Acta Cryst. 2018, B74, 681-692). In vacuo DFT geometry optimizations (improper axial water ligand orientation) are compared against the periodic ones. The singlet state is found to be energetically preferred. J coupling of (I) becomes underestimated for all ab initio methods used, when compared to experiment. It is concluded that the strength of the direct M─M interactions correlates closely with the J coupling magnitude at a given level of theory. The double potential well character of (II) and of the dehydrated form of (II) are considered with respect to the Cr─Cr distance. The physical effective bond order of the metal-metal interaction is small (below 0.1 e) in (I) and moderate (0.4 e) in (II). The CASSCF results overestimate the electron density of the metal-metal bond critical point by 20% and 50% in (I) and (II), respectively, when compared to the multipole model. © 2019 Wiley Periodicals, Inc.
Keywords: QTAIM analysis; electronic structure; metal-metal interaction; paddle-wheel; population analysis.
© 2019 Wiley Periodicals, Inc.