Excitation Energies of Embedded Chromophores from Frozen-Density Embedding Theory Using State-Specific Electron Densities of the Environment

Starting from the Perdew–Levy theorem on extrema of the Hohenberg–Kohn functional, the expression for the vertical excitation energy is derived within the formal framework of Frozen-Density Embedding Theory (FDET) that makes it possible to use state-specific electron densities of the environment (ρB) of an embedded species. The derived general expression involves the embedded wave functions for ground and excited states that are orthogonal and is exact up to quadratic terms in the appropriate density expansion. It can be applied in practice using various methods differing in the treatment of the electron–electron correlation for embedded electrons, the method to evaluate different contributions to the excitation energy, the method to generate state-specific ρB, and the approximation used for the non-electrostatic component of the FDET embedding potential. The derived expression is applied for 47 local excitations in 10 embedded organic chromophores. The explicit treatment of the differential polarization of ρB improves indeed the accuracy of the excitation energy as compared to the implicit treatment in which the same ρB is used for all states of embedded chromophore. For 47 local excitations in 10 embedded organic chromophores, the average absolute errors in excitation energies drop from 0.04 to 0.03 eV and their standard deviations from 0.032 to 0.025 eV, respectively. The maximal errors show similar trends