Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study

We present a comprehensive analysis of the electronic structure of the PF6¯anion, a prototypical octahedral molecular system with high Oh symmetry.Using symmetry-adapted linear combinations of atomic orbitals and grouptheoretical techniques, we construct molecular orbitals and provide a systematic c...

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Autores: M. Masanja, Paul, Tarimo, Esther J., Rao, P. V. Kanaka, Singh, Vijay, Mwankemwa, Bernard, Junquera Quintana, Francisco Javier|||0000-0002-9957-8982
Tipo de recurso: artículo
Fecha de publicación:2026
País:España
Institución:Universidad de Cantabria (UC)
Repositorio:UCrea Repositorio Abierto de la Universidad de Cantabria
Idioma:inglés
OAI Identifier:oai:dnet:ucreareposit::c52304cf2d6265e37256fe8e06215146
Acceso en línea:https://hdl.handle.net/10902/40040
Access Level:acceso abierto
Palabra clave:Density functional (DFT)
Electronic structure
Group theory
PF6-
Wanniers functions
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spelling Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case studyM. Masanja, PaulTarimo, Esther J.Rao, P. V. KanakaSingh, VijayMwankemwa, BernardJunquera Quintana, Francisco Javier|||0000-0002-9957-8982Density functional (DFT)Electronic structureGroup theoryPF6-Wanniers functionsWe present a comprehensive analysis of the electronic structure of the PF6¯anion, a prototypical octahedral molecular system with high Oh symmetry.Using symmetry-adapted linear combinations of atomic orbitals and grouptheoretical techniques, we construct molecular orbitals and provide a systematic classification according to irreducible representations of the Oh point group. The role of the P-centered 3s, 3p, and 3d orbitals, together with the symmetry-adapted 2s and 2p orbitals of the six surrounding fluorine atoms, is explicitly analyzed. The electronic structure is described both within the theory of molecular orbitals and with the picture based on sp3d2 hybridization. Maximally localized Wannier functions derived from first-principles density functional theory calculations using the siesta and wannier90 codes are computed. The constructed Wannier functions accurately reflect the expected molecular symmetries and provide a natural minimal basis for tight-binding and second-principles modeling. A detailed comparison is made between bonding, nonbonding, and antibonding orbitals, as well as their energetic ordering. Our results demonstrate the interplay between symmetry, bonding, and electronic structure in molecular systems with high cubic symmetry and set the stage for the development of accurate minimal models for such systems.The author(s) declared that financial support was received for this work and/or its publication. We acknowledge support from Erasmus+ KA-107 action and the ViceRector for of Internationalisation and Global Engagement the University of Cantabria. JJ acknowledges financial support from Grant No. PID2022-139776NB-C63 funded by MCIN/AEI/10.13039/501100011033 and by ERDF “A way of making Europe” by the European Union.Frontiers Media S.A.Universidad de Cantabria20262026-01-01journal articlehttp://purl.org/coar/resource_type/c_6501NAhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43info:eu-repo/semantics/articlehttps://hdl.handle.net/10902/40040Frontiers in Physics, 2026, 14, 1764641reponame:UCrea Repositorio Abierto de la Universidad de Cantabriainstname:Universidad de Cantabria (UC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:dnet:ucreareposit::c52304cf2d6265e37256fe8e062151462026-06-02T12:39:31Z
dc.title.none.fl_str_mv Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
title Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
spellingShingle Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
M. Masanja, Paul
Density functional (DFT)
Electronic structure
Group theory
PF6-
Wanniers functions
title_short Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
title_full Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
title_fullStr Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
title_full_unstemmed Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
title_sort Symmetry, bonding, and wannier function construction in the PF¯6 molecule: a first-principles case study
dc.creator.none.fl_str_mv M. Masanja, Paul
Tarimo, Esther J.
Rao, P. V. Kanaka
Singh, Vijay
Mwankemwa, Bernard
Junquera Quintana, Francisco Javier|||0000-0002-9957-8982
author M. Masanja, Paul
author_facet M. Masanja, Paul
Tarimo, Esther J.
Rao, P. V. Kanaka
Singh, Vijay
Mwankemwa, Bernard
Junquera Quintana, Francisco Javier|||0000-0002-9957-8982
author_role author
author2 Tarimo, Esther J.
Rao, P. V. Kanaka
Singh, Vijay
Mwankemwa, Bernard
Junquera Quintana, Francisco Javier|||0000-0002-9957-8982
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Universidad de Cantabria
dc.subject.none.fl_str_mv Density functional (DFT)
Electronic structure
Group theory
PF6-
Wanniers functions
topic Density functional (DFT)
Electronic structure
Group theory
PF6-
Wanniers functions
description We present a comprehensive analysis of the electronic structure of the PF6¯anion, a prototypical octahedral molecular system with high Oh symmetry.Using symmetry-adapted linear combinations of atomic orbitals and grouptheoretical techniques, we construct molecular orbitals and provide a systematic classification according to irreducible representations of the Oh point group. The role of the P-centered 3s, 3p, and 3d orbitals, together with the symmetry-adapted 2s and 2p orbitals of the six surrounding fluorine atoms, is explicitly analyzed. The electronic structure is described both within the theory of molecular orbitals and with the picture based on sp3d2 hybridization. Maximally localized Wannier functions derived from first-principles density functional theory calculations using the siesta and wannier90 codes are computed. The constructed Wannier functions accurately reflect the expected molecular symmetries and provide a natural minimal basis for tight-binding and second-principles modeling. A detailed comparison is made between bonding, nonbonding, and antibonding orbitals, as well as their energetic ordering. Our results demonstrate the interplay between symmetry, bonding, and electronic structure in molecular systems with high cubic symmetry and set the stage for the development of accurate minimal models for such systems.
publishDate 2026
dc.date.none.fl_str_mv 2026
2026-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
NA
http://purl.org/coar/version/c_be7fb7dd8ff6fe43
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/10902/40040
url https://hdl.handle.net/10902/40040
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Frontiers Media S.A.
publisher.none.fl_str_mv Frontiers Media S.A.
dc.source.none.fl_str_mv Frontiers in Physics, 2026, 14, 1764641
reponame:UCrea Repositorio Abierto de la Universidad de Cantabria
instname:Universidad de Cantabria (UC)
instname_str Universidad de Cantabria (UC)
reponame_str UCrea Repositorio Abierto de la Universidad de Cantabria
collection UCrea Repositorio Abierto de la Universidad de Cantabria
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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