Frozen-Density Embedding Theory based simulations with experimental electron densities

TL;DR

This paper introduces the first application of Frozen-Density Embedding Theory (FDET) using experimental electron densities from X-ray diffraction data to perform multi-level simulations and calculate excitation energies in molecular clusters.

Contribution

It demonstrates the novel use of experimental electron densities within FDET for multi-level simulations and excitation energy calculations.

Findings

Experimental densities are suitable for FDET simulations.

FDET can accurately derive excitation energies in molecular clusters.

First-time application of FDET with experimental electron densities.

Abstract

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.