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N-representability of the target density in Frozen-Density Embedding Theory based methods: Numerical significance and its relation to electronic polarization

Published inThe Journal of chemical physics, vol. 157, no. 6, p. 1-10; 064108
Publication date2022-08-14
First online date2022-08-10
Abstract

The accuracy of any observable derived from multi-scale simulations based on Frozen-Density Embedding Theory (FDET) is affected by two inseparable factors: (i) the approximation for the ExcTnad[ρA,ρB] component of the FDET energy functional and (ii) the choice of the density ρB(r) for which the FDET eigenvalue equation for the embedded wavefunction is solved. A procedure is proposed to estimate the relative significance of these two factors. Numerical examples are given for four weakly bound intermolecular complexes. It is shown that the violation of the non-negativity condition is the principal source of error in the FDET energy if ρB is the density of the isolated environment, i.e., it is generated without taking into account the interactions with the embedded species. Reduction of both the magnitude of the violation of the non-negativity condition and the error in the FDET energy can be pragmatically achieved by means of the explicit treatment of the electronic polarization of the environment.

Keywords
  • Density functional theory
  • Electronic structure methods
  • Excitation energies
  • Correlation energy
  • Mulliken population analysis
  • Condensed matter theories and models
  • Electrostatics
  • Multiscale methods
  • Intermolecular forces
  • Variational methods
Citation (ISO format)
RICARDI, Niccolo, GONZALEZ ESPINOZA, Cristina, WESOLOWSKI, Tomasz Adam. N-representability of the target density in Frozen-Density Embedding Theory based methods: Numerical significance and its relation to electronic polarization. In: The Journal of chemical physics, 2022, vol. 157, n° 6, p. 1–10. doi: 10.1063/5.0095566
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ISSN of the journal0021-9606
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