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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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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2021
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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. |
format | Online Article Text |
id | pubmed-8000561 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
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 |