Electronic Structure Calculations: Density Functional Methods for Spin Polarization, Charge Transfer, and Solvent Effects in Transition Metal Complexes
Аннотация:Results of density functional calculations are presented for 16 mononuclear transition metal complexes (high-spin and low-spin systems), and 11 bridged dinuclear complexes. The dinuclear complexes are spin-coupled and the broken symmetry method is quite effective for predicting optimal geometries. The local Vosko-Stoll (VS) exchange-correlation potential predicts both mononuclear and dinuclear geometries well. Redox potentials for the entire first row transition metal ion series M2+,3+ in aqueous solution are calculated by metal-hexa-aquo ion calculations with extrapolation from calculations on Mn2+,3+ and Fe2+,3+ . Both experimental trends and energies are well portrayed (largest error about 350 mV out of a 2000 mV range). Overall, the long range environment is more critical for energetics than for geometries where the local coordination environment dominates.
