Strong electron correlations in cobalt valence tautomers

Abstract

We have examined cobalt based valence tautomer molecules such as Co(SQ)2(phen) using density functional theory (DFT) and variational configuration interaction (VCI) approaches based upon a model Hamiltonian. Our DFT results extend earlier work by finding a reduced total energy gap (order 0.6 eV) between high-temperature and low-temperature states when we fully relax the coordinates (relative to experimental ones). Furthermore, we demonstrate that a charge transfer picture based upon formal valence arguments succeeds qualitatively while failing quantitatively due to strong covalency between the Co 3d orbitals and ligand p orbitals. With the VCI approach, we argue that the high-temperature, high spin phase is strongly mixed valent, with about 30% admixture of Co (III) into the predominantly Co(II) ground state. We confirm this mixed valence through a fit to the XANES spectra. Moreover, the strong electron correlations of the mixed valent phase provide an energy lowering of about 0.2–0.3 eV of the high-temperature phase relative to the low-temperature one. Finally, we use the domain model to account for the extraordinarily large entropy and enthalpy values associated with the transition.