@Article{MolPhys_114_1199,
author = {A. Zech and F. Aquilante and T.A. Wesolowski},
title = {{Homogeneity properties of the embedding potential in frozen-density embedding theory}},
journal= {Mol. Phys.},
ISSN = {0026-8976},
volume= {114},
number= {7-8},
pages = {1199-1206},
url = {http://www.tandfonline.com/doi/full/10.1080/00268976.2015.1125027#abstract},
eprint= {http://www.unige.ch/sciences/chifi/publis/refs_pdf/ref01500.pdf},
doi= {10.1080/00268976.2015.1125027},
keywords= {embedding;multi-level simulations;density functional theory;homogeneity;frozen-density embedding theory},
abstract = {{In numerical simulations, based on frozen-density embedding theory, the independent variables describing the total system are the embedded wave function ($\Psi_{{\em A}}$) and the density {\em $\rho_{B}$(r)} representing the environment. Due to inhomogeneity of the non-electrostatic component of the total energy: {\em E}$^{nad}${\em $_{xcT}$}[{\em $\rho_{A}$},{\em $\rho_{B}$}] â â« {\em $\rho_{A}$}(r) ($\delta${\em E}$^{nad}${\em $_{xcT}$}[{\em $\rho$}{\em $_{A}$},{\em $\rho_{B}$}] / $\delta${\em $\rho$A}(r)) dr , the expectation value of the embedding potential is not equal to the corresponding component of the total energy. The differences $\Delta$$^{nad}${\em $_{xcT}$} = {\em E}$^{nad}${\em $_{xcT}$}[{\em $\rho_{A}$},{\em $\rho_{B}$}] {\frac{ }{ }} â« {\em $\rho_{A}$}(r) ($\delta${\em E}$^{nad}${\em $_{xcT}$}[{\em $\rho$}{\em $_{A}$},{\em $\rho_{B}$}] / $\delta${\em $\rho_{A}$}(r)) dr are evaluated using local and semi-local approximations for the functional {\em E}$^{nad}_{{\em xcT}}$[$\rho_{{\em A}}$, $\rho_{{\em B}}$] in two model systems representing embedded species weakly interacting with the environment. It is found that $\Delta$$^{nad}_{{\em xcT}}$ is typically one order of magnitude smaller than {\em E}$^{nad}_{{\em xcT}}$[$\rho_{{\em A}}$, $\rho_{{\em B}}$] and decreases with the overlap between {\em $\rho_{A}$}(r) and {\em $\rho_{B}$}(r) . The kinetic- and exchange-correlation contributions to $\Delta$$^{nad}_{{\em xcT}}$ cancel partially reducing its magnitude to {\em m}Hartrees. Compared to local approximation for {\em E}$^{nad}_{{\em xcT}}$[$\rho_{{\em A}}$, $\rho_{{\em B}}$], the inhomogeneity is more pronounced in semi-local functionals.}},
year = {2016}
}