Embedding-theory-based simulations using experimental electron densities for the environment

The basic idea of frozen-density embedding theory (FDET) is the constrained minimization of the Hohenberg–Kohn density functional E (HK)[ρ] performed using the auxiliary functional [Image: see text], where Ψ(A) is the embedded N (A)-electron wavefunction and ρ(B)(r) is a non-negative function in real space integrating to a given number of electrons N (B). This choice of independent variables in the total energy functional [Image: see text] makes it possible to treat the corresponding two components of the total density using different methods in multi-level simulations. The application of FDET using ρ(B)(r) reconstructed from X-ray diffraction data for a molecular crystal is demonstrated for the first time. For eight hydrogen-bonded clusters involving a chromophore (represented as Ψ(A)) and the glycylglycine molecule [represented as ρ(B)(r)], FDET is used to derive excitation energies. It is shown that experimental densities are suitable for use as ρ(B)(r) in FDET-based simulations.