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Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory

This work presents a method to move beyond the recently introduced atomic fragment approximation. Like the bare atomic fragment approach, the new method is an ab initio, parameter-free, orbital-free implementation of density functional theory based on the bifunctional formalism that treats the poten...

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Detalles Bibliográficos
Autor principal: Finzel, Kati
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8000561/
https://www.ncbi.nlm.nih.gov/pubmed/33799716
http://dx.doi.org/10.3390/molecules26061539
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author Finzel, Kati
author_facet Finzel, Kati
author_sort Finzel, Kati
collection PubMed
description This work presents a method to move beyond the recently introduced atomic fragment approximation. Like the bare atomic fragment approach, the new method is an ab initio, parameter-free, orbital-free implementation of density functional theory based on the bifunctional formalism that treats the potential and the electron density as two separate variables, and provides access to the Kohn–Sham Pauli kinetic energy for an appropriately chosen Pauli potential. In the present ansatz, the molecular Pauli potential is approximated by the sum of the bare atomic fragment approach, and a so-called deformation potential that takes the interaction between the atoms into account. It is shown that this model can reproduce the bond-length contraction due to multiple bonding within the list of second-row homonuclear dimers. The present model only relies on the electron densities of the participating atoms, which themselves are represented by a simple monopole expansion. Thus, the bond-length contraction can be rationalized without referring to the angular quantum numbers of the participating atoms.
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spelling pubmed-80005612021-03-28 Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory Finzel, Kati Molecules Article This work presents a method to move beyond the recently introduced atomic fragment approximation. Like the bare atomic fragment approach, the new method is an ab initio, parameter-free, orbital-free implementation of density functional theory based on the bifunctional formalism that treats the potential and the electron density as two separate variables, and provides access to the Kohn–Sham Pauli kinetic energy for an appropriately chosen Pauli potential. In the present ansatz, the molecular Pauli potential is approximated by the sum of the bare atomic fragment approach, and a so-called deformation potential that takes the interaction between the atoms into account. It is shown that this model can reproduce the bond-length contraction due to multiple bonding within the list of second-row homonuclear dimers. The present model only relies on the electron densities of the participating atoms, which themselves are represented by a simple monopole expansion. Thus, the bond-length contraction can be rationalized without referring to the angular quantum numbers of the participating atoms. MDPI 2021-03-11 /pmc/articles/PMC8000561/ /pubmed/33799716 http://dx.doi.org/10.3390/molecules26061539 Text en © 2021 by the author. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Finzel, Kati
Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory
title Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory
title_full Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory
title_fullStr Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory
title_full_unstemmed Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory
title_short Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory
title_sort deformation potentials: towards a systematic way beyond the atomic fragment approach in orbital-free density functional theory
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8000561/
https://www.ncbi.nlm.nih.gov/pubmed/33799716
http://dx.doi.org/10.3390/molecules26061539
work_keys_str_mv AT finzelkati deformationpotentialstowardsasystematicwaybeyondtheatomicfragmentapproachinorbitalfreedensityfunctionaltheory