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Density dependent embedding potentials for piecewise exact densities

Chemical Physics 2025-07-02 v2

Abstract

Frozen Density Embedding Theory (FDET) [Wesolowski {\it Phys. Rev. A} {\bf 77}, 012504 (2008)] provides the interpretation of the eigenvalue equations for an embedded NN'-electron wavefunction, in which the embedding operator is multiplicative, as the Euler-Lagrange equation corresponding to the constrained minimisation of the Hohenberg-Kohn energy functional. The constraint is given by a non-negative function integrating to an integer NN>0N-N'>0 with NN being the total number of electrons in the whole system (minρr(ρ(r)ρ2(r)EvHK[ρ]=EvHK[ρ1FDET+ρ2]EHK[ρvo]=Evo\min_{\rho\rightarrow\forall_{\mathbf{r}}\big(\rho({\mathbf r})\ge \rho_2({\mathbf r}\big)} E^{HK}_v[\rho]=E^{HK}_v[\rho_1^{FDET}+\rho_2]\ge E^{HK}[\rho_v^{o}]=E^o_v). The exact FDET eigenvalue equations are analysed for ρ2\rho_2 such that it is equal to the exact ground-state density ρvo(r)\rho_v^{o}({\mathbf r}) in some measurable volume. It is shown that, the stationary (ρ1FDET\rho_1^{FDET}) obtained from the FDET eigenvalue equations - if it exists - differs from ρ1o=ρvoρ2\rho_1^o=\rho_v^{o}-\rho_2 leading to the sharp inequality EHK[ρ1FDET+ρ2]>EvoE^{HK}[\rho_1^{FDET}+\rho_2]> E^o_v for such densities ρ2\rho_2. The result is discussed in the context of subsystem DFT, pseudopotential theory, and exact density-dependent embedding potentials.

Keywords

Cite

@article{arxiv.2506.08744,
  title  = {Density dependent embedding potentials for piecewise exact densities},
  author = {Tomasz Adam Wesolowski},
  journal= {arXiv preprint arXiv:2506.08744},
  year   = {2025}
}
R2 v1 2026-07-01T03:09:00.696Z