Towards a universal scaling method for predicting equilibrium constants of polyoxometalates

The computational prediction of equilibrium constants is still an open problem for a wide variety of relevant chemical systems. In particular, acid dissociation constants (pKa) are an essential asset in biological, synthetic and industrial chemistry whose prediction encounters several difficulties,...

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Detalles Bibliográficos
Autores: Buils, Jordi, Garay-Ruiz, Diego, Petrus, Enric, Segado-Centellas, Mireia, Bo, Carles
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/482381
Acceso en línea:http://hdl.handle.net/2072/482381
Access Level:acceso abierto
Palabra clave:Química
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spelling Towards a universal scaling method for predicting equilibrium constants of polyoxometalatesBuils, JordiGaray-Ruiz, DiegoPetrus, EnricSegado-Centellas, MireiaBo, CarlesQuímica54The computational prediction of equilibrium constants is still an open problem for a wide variety of relevant chemical systems. In particular, acid dissociation constants (pKa) are an essential asset in biological, synthetic and industrial chemistry whose prediction encounters several difficulties, requiring the development of novel strategies. The self-assembly of polyoxometalates (POMs) is another complex problem where acid-base reactions play a central role; the successful prediction of the formation constants of these structures is intimately linked with the limitations of pKa determination. Our methodology POMSimulator enables the prediction of these polyoxometalate formation constants from Density Functional Theory (DFT) calculations, using the experimental Kf values available in the literature to fit the resulting predictions. In this work, we carry out a systematic analysis of a very large number of POM formation constants already predicted through the application of POMSimulator. We then propose a universal scaling scheme for the adjustment of the DFT-based formation constants of POMs, relying on a linear scaling of the form y = mx + b. Here, the slope (m) is a constant parameter – hence, universal towards the nature of the polyoxometalate and the calculation method. The intercept (b), in contrast, is a system-dependent parameter that can be predicted with a multi-linear regression model trained with statistical aggregates of the non-scaled formation constants. Thus, we are able to successfully predict the speciation and phase diagrams of POM systems for which available experimental data are minimal, as well as provide a general scaling scheme that might be extended to other kinds of chemical systems.info:eu-repo/semantics/publishedVersionRoyal Society of Chemistry2025info:eu-repo/semantics/article9 p.application/pdfhttp://hdl.handle.net/2072/482381RECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésSpanish Ministry of Science, Innovation and Universities MCIU/AEI/10.13039/501100011033 (PID2023-153344NB-I00 and CEX2019-000925-S)European Union NextGeneration EU/PRTR (TED2021-132850B-I00)ICIQ FoundationCERCA Program/Generalitat de CatalunyaAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:2072/4823812026-05-29T05:05:01Z
dc.title.none.fl_str_mv Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
title Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
spellingShingle Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
Buils, Jordi
Química
54
title_short Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
title_full Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
title_fullStr Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
title_full_unstemmed Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
title_sort Towards a universal scaling method for predicting equilibrium constants of polyoxometalates
dc.creator.none.fl_str_mv Buils, Jordi
Garay-Ruiz, Diego
Petrus, Enric
Segado-Centellas, Mireia
Bo, Carles
author Buils, Jordi
author_facet Buils, Jordi
Garay-Ruiz, Diego
Petrus, Enric
Segado-Centellas, Mireia
Bo, Carles
author_role author
author2 Garay-Ruiz, Diego
Petrus, Enric
Segado-Centellas, Mireia
Bo, Carles
author2_role author
author
author
author
dc.subject.none.fl_str_mv Química
54
topic Química
54
description The computational prediction of equilibrium constants is still an open problem for a wide variety of relevant chemical systems. In particular, acid dissociation constants (pKa) are an essential asset in biological, synthetic and industrial chemistry whose prediction encounters several difficulties, requiring the development of novel strategies. The self-assembly of polyoxometalates (POMs) is another complex problem where acid-base reactions play a central role; the successful prediction of the formation constants of these structures is intimately linked with the limitations of pKa determination. Our methodology POMSimulator enables the prediction of these polyoxometalate formation constants from Density Functional Theory (DFT) calculations, using the experimental Kf values available in the literature to fit the resulting predictions. In this work, we carry out a systematic analysis of a very large number of POM formation constants already predicted through the application of POMSimulator. We then propose a universal scaling scheme for the adjustment of the DFT-based formation constants of POMs, relying on a linear scaling of the form y = mx + b. Here, the slope (m) is a constant parameter – hence, universal towards the nature of the polyoxometalate and the calculation method. The intercept (b), in contrast, is a system-dependent parameter that can be predicted with a multi-linear regression model trained with statistical aggregates of the non-scaled formation constants. Thus, we are able to successfully predict the speciation and phase diagrams of POM systems for which available experimental data are minimal, as well as provide a general scaling scheme that might be extended to other kinds of chemical systems.
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/482381
url http://hdl.handle.net/2072/482381
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Spanish Ministry of Science, Innovation and Universities MCIU/AEI/10.13039/501100011033 (PID2023-153344NB-I00 and CEX2019-000925-S)
European Union NextGeneration EU/PRTR (TED2021-132850B-I00)
ICIQ Foundation
CERCA Program/Generalitat de Catalunya
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 9 p.
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812455

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