Dynamic-then-Static Approach for Core Excitations of Open-Shell Molecules

Delta self-consistent-field methods are widely used in studies of electronically excited states. However, the nonaufbau determinants are generally spin-contaminated. Here, we describe a general approach for spin-coupling interactions of open-shell molecules, making use of multistate density functional theory (MSDFT). In particular, the effective exchange integrals that determine spin coupling are obtained by enforcing the multiplet degeneracy of the S+1 state in the M-S = S manifold. Consequently, they are consistent with the energy of the high-spin state that is adequately treated by Kohn-Sham density functional theory (DFT) and, thereby, free of double counting of correlation. The method was applied to core excitations of open-shell molecules and compared with those by spin-adapted time-dependent DFT. An excellent agreement with experiment was found employing the BLYP functional and aug-cc-pCVQZ basis set. Overall, MSDFT provides an effective combination of the strengths of DFT and wave function theory to achieve efficiency and accuracy.

Automated summary

Delta self-consistent-field methods are widely used in studies of electronically excited states, but often suffer from spin contamination. This study presents a general approach using MSDFT to handle spin-coupling interactions in open-shell molecules, providing effective combination of DFT and wave function theory for efficiency and accuracy in core excitations. Experiments showed excellent agreement with the proposed method, demonstrating its effectiveness in avoiding double counting of correlation effects.