Calculation of Exchange Coupling Constants in Triply-Bridged Dinuclear Cu(II) Compounds Based on Spin-Flip Constricted Variational Density Functional Theory

The performance of the second-order spin-flip constricted
variational
density functional theory (SF-CV(2)-DFT) for the calculation of the
exchange coupling constant (J) is assessed by application
to a series of triply bridged Cu­(II) dinuclear complexes. A comparison
of the J values based on SF-CV(2)-DFT with those
obtained by the broken symmetry (BS) DFT method and experiment is
provided. It is demonstrated that our methodology constitutes a viable
alternative to the BS-DFT method. The strong dependence of the calculated
exchange coupling constants on the applied functionals is demonstrated.
Both SF-CV(2)-DFT and BS-DFT affords the best agreement with experiment
for hybrid functionals.