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

• DOI: 10.1021/acs.jctc.0c00208
• Publication Date: 2020-07-16T16:40:29Z
• Authors: Zexing Qu; Yingjin Ma
• Keywords: 01 natural sciences; 0104 chemical sciences

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