Variational Multistate Density Functional Theory for a Balanced Treatment of Static and Dynamic Correlations

Here, an approach to variational multistate density functional theory (vMSDFT) is explored. In this approach, the Kohn-Sham orbitals as well as configuration coefficients were simultaneously optimized, thus yielding a full variational minimum. Furthermore, this work also proposes two important improvements on the MSDFT framework. First, a "point-to-point correction" is used to correct the static correlation present in the DFT framework. Therefore, double counting of static correlation in vMSDFT is mitigated. Second, a general form to construct the transition density functional in the vMSDFT framework is proposed, which allows for the properties of vMSDFT wave functions to be standardized to the complete active space self-consistent field properties. The utility of vMSDFT is illustrated on molecular systems of interest including bond breaking, diradicals, excited states, and conical intersections. The numerical results suggest that the accuracy of vMSDFT is in close agreement with the high-level multireference methods.