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 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.
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14 August 2022
Research Article|
August 10 2022
N-representability of the target density in Frozen-Density Embedding Theory based methods: Numerical significance and its relation to electronic polarization
Niccolò Ricardi
;
Niccolò Ricardi
a)
(Conceptualization, Data curation, Formal analysis, Investigation, Software, Writing – original draft, Writing – review & editing)
Department of Physical Chemistry, University of Geneva
, Geneva, Switzerland
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Cristina E. González-Espinoza
;
Cristina E. González-Espinoza
b)
(Conceptualization, Data curation, Formal analysis, Software, Writing – original draft, Writing – review & editing)
Department of Physical Chemistry, University of Geneva
, Geneva, Switzerland
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Tomasz Adam Wesołowski
Tomasz Adam Wesołowski
c)
(Conceptualization, Formal analysis, Funding acquisition, Methodology, Writing – original draft, Writing – review & editing)
Department of Physical Chemistry, University of Geneva
, Geneva, Switzerland
c)Author to whom correspondence should be addressed: Tomasz.Wesolowski@unige.ch
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a)
Electronic mail: Niccolo.Ricardi@unige.ch
b)
Electronic mail: Cristina.GonzalezEspinoza@unige.ch
c)Author to whom correspondence should be addressed: Tomasz.Wesolowski@unige.ch
J. Chem. Phys. 157, 064108 (2022)
Article history
Received:
April 11 2022
Accepted:
July 04 2022
Citation
Niccolò Ricardi, Cristina E. González-Espinoza, Tomasz Adam Wesołowski; N-representability of the target density in Frozen-Density Embedding Theory based methods: Numerical significance and its relation to electronic polarization. J. Chem. Phys. 14 August 2022; 157 (6): 064108. https://doi.org/10.1063/5.0095566
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