The basic idea of Frozen-Density Embedding Theory (FDET) is the constrained minimisation of the Hohenberg-Kohn density functional $E^{ HK}[\rho]$ performed using the auxiliary functional $E_{ v_{ AB}}^{ FDET}[\Psi_A,\rho_B]$, where $\Psi_A$ is the embedded $N_A$-electron wave-function and $\rho_B(\vec{ \mathrm{ r}})$ 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 $E_{ v_{ AB}}^{ FDET}[\Psi_A,\rho_B]$ makes it possible to treat the corresponding two components of the total density using different methods in multi-level simulations. We demonstrate, for the first time, the applications of FDET using $\rho_B(\vec{ \mathrm{ r}})$ reconstructed from X-ray diffraction data on a molecular crystal. For eight hydrogen-bonded clusters involving a chromophore (represented with $\Psi_A$) and the glycylglycine molecule (represented as $\rho_B(\vec{ \mathrm{ r}})$), FDET is used to derive excitation energies. It is shown that experimental densities are suitable to be used as $\rho_B(\vec{ \mathrm{ r}})$ in FDET based simulations.
Categories: physics.chem-ph
