Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks

Autores
Oviedo, María Belén; Ilawe, Niranjan V.; Wong, Bryan M.
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We present a detailed analysis of nonempirically tuned range-separated functionals, with both short- and long-range exchange, for calculating the static linear polarizability and second hyperpolarizabilities of various polydiacetylene (PDA) and polybutatriene (PBT) oligomers. Contrary to previous work on these systems, we find that the inclusion of some amount of short-range exchange does improve the accuracy of the computed polarizabilities and second hyperpolarizabilities. Most importantly, in contrast to prior studies on these oligomers, we find that the lowest-energy electronic states for PBT are not closed-shell singlets, and enhanced accuracy with range-separated DFT can be obtained by allowing the system to relax to a lower-energy broken-symmetry solution. Both the computed polarizabilities and second hyperpolarizabilities for PBT are significantly improved with these broken-symmetry solutions when compared to previously published and current benchmarks. In addition to these new analyses, we provide new large-scale CCSD(T) and explicitly correlated CCSD(T)-F12 benchmarks for the PDA and PBT systems, which comprise the most complete and accurate calculations of linear polarizabilities and second hyperpolarizabilities on these systems to date. These new CCSD(T) and CCSD(T)-F12 benchmarks confirm our DFT results and emphasize the importance of broken-symmetry effects when calculating polarizabilities and hyperpolarizabilties of π-conjugated chains.
Fil: Oviedo, María Belén. University Of California Riverside; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ilawe, Niranjan V.. University Of California Riverside; Estados Unidos
Fil: Wong, Bryan M.. University Of California Riverside; Estados Unidos
Materia
Dft
Polarizabilities
Broken Symmetry
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/54163

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spelling Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) BenchmarksOviedo, María BelénIlawe, Niranjan V.Wong, Bryan M.DftPolarizabilitiesBroken Symmetryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We present a detailed analysis of nonempirically tuned range-separated functionals, with both short- and long-range exchange, for calculating the static linear polarizability and second hyperpolarizabilities of various polydiacetylene (PDA) and polybutatriene (PBT) oligomers. Contrary to previous work on these systems, we find that the inclusion of some amount of short-range exchange does improve the accuracy of the computed polarizabilities and second hyperpolarizabilities. Most importantly, in contrast to prior studies on these oligomers, we find that the lowest-energy electronic states for PBT are not closed-shell singlets, and enhanced accuracy with range-separated DFT can be obtained by allowing the system to relax to a lower-energy broken-symmetry solution. Both the computed polarizabilities and second hyperpolarizabilities for PBT are significantly improved with these broken-symmetry solutions when compared to previously published and current benchmarks. In addition to these new analyses, we provide new large-scale CCSD(T) and explicitly correlated CCSD(T)-F12 benchmarks for the PDA and PBT systems, which comprise the most complete and accurate calculations of linear polarizabilities and second hyperpolarizabilities on these systems to date. These new CCSD(T) and CCSD(T)-F12 benchmarks confirm our DFT results and emphasize the importance of broken-symmetry effects when calculating polarizabilities and hyperpolarizabilties of π-conjugated chains.Fil: Oviedo, María Belén. University Of California Riverside; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ilawe, Niranjan V.. University Of California Riverside; Estados UnidosFil: Wong, Bryan M.. University Of California Riverside; Estados UnidosAmerican Chemical Society2016-08-22info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/54163Oviedo, María Belén; Ilawe, Niranjan V.; Wong, Bryan M.; Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks; American Chemical Society; Journal of Chemical Theory and Computation; 12; 8; 22-8-2016; 3593-36021549-9618CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jctc.6b00360info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.6b00360info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:38:16Zoai:ri.conicet.gov.ar:11336/54163instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:38:17.18CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
title Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
spellingShingle Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
Oviedo, María Belén
Dft
Polarizabilities
Broken Symmetry
title_short Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
title_full Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
title_fullStr Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
title_full_unstemmed Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
title_sort Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
dc.creator.none.fl_str_mv Oviedo, María Belén
Ilawe, Niranjan V.
Wong, Bryan M.
author Oviedo, María Belén
author_facet Oviedo, María Belén
Ilawe, Niranjan V.
Wong, Bryan M.
author_role author
author2 Ilawe, Niranjan V.
Wong, Bryan M.
author2_role author
author
dc.subject.none.fl_str_mv Dft
Polarizabilities
Broken Symmetry
topic Dft
Polarizabilities
Broken Symmetry
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We present a detailed analysis of nonempirically tuned range-separated functionals, with both short- and long-range exchange, for calculating the static linear polarizability and second hyperpolarizabilities of various polydiacetylene (PDA) and polybutatriene (PBT) oligomers. Contrary to previous work on these systems, we find that the inclusion of some amount of short-range exchange does improve the accuracy of the computed polarizabilities and second hyperpolarizabilities. Most importantly, in contrast to prior studies on these oligomers, we find that the lowest-energy electronic states for PBT are not closed-shell singlets, and enhanced accuracy with range-separated DFT can be obtained by allowing the system to relax to a lower-energy broken-symmetry solution. Both the computed polarizabilities and second hyperpolarizabilities for PBT are significantly improved with these broken-symmetry solutions when compared to previously published and current benchmarks. In addition to these new analyses, we provide new large-scale CCSD(T) and explicitly correlated CCSD(T)-F12 benchmarks for the PDA and PBT systems, which comprise the most complete and accurate calculations of linear polarizabilities and second hyperpolarizabilities on these systems to date. These new CCSD(T) and CCSD(T)-F12 benchmarks confirm our DFT results and emphasize the importance of broken-symmetry effects when calculating polarizabilities and hyperpolarizabilties of π-conjugated chains.
Fil: Oviedo, María Belén. University Of California Riverside; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ilawe, Niranjan V.. University Of California Riverside; Estados Unidos
Fil: Wong, Bryan M.. University Of California Riverside; Estados Unidos
description We present a detailed analysis of nonempirically tuned range-separated functionals, with both short- and long-range exchange, for calculating the static linear polarizability and second hyperpolarizabilities of various polydiacetylene (PDA) and polybutatriene (PBT) oligomers. Contrary to previous work on these systems, we find that the inclusion of some amount of short-range exchange does improve the accuracy of the computed polarizabilities and second hyperpolarizabilities. Most importantly, in contrast to prior studies on these oligomers, we find that the lowest-energy electronic states for PBT are not closed-shell singlets, and enhanced accuracy with range-separated DFT can be obtained by allowing the system to relax to a lower-energy broken-symmetry solution. Both the computed polarizabilities and second hyperpolarizabilities for PBT are significantly improved with these broken-symmetry solutions when compared to previously published and current benchmarks. In addition to these new analyses, we provide new large-scale CCSD(T) and explicitly correlated CCSD(T)-F12 benchmarks for the PDA and PBT systems, which comprise the most complete and accurate calculations of linear polarizabilities and second hyperpolarizabilities on these systems to date. These new CCSD(T) and CCSD(T)-F12 benchmarks confirm our DFT results and emphasize the importance of broken-symmetry effects when calculating polarizabilities and hyperpolarizabilties of π-conjugated chains.
publishDate 2016
dc.date.none.fl_str_mv 2016-08-22
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/54163
Oviedo, María Belén; Ilawe, Niranjan V.; Wong, Bryan M.; Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks; American Chemical Society; Journal of Chemical Theory and Computation; 12; 8; 22-8-2016; 3593-3602
1549-9618
CONICET Digital
CONICET
url http://hdl.handle.net/11336/54163
identifier_str_mv Oviedo, María Belén; Ilawe, Niranjan V.; Wong, Bryan M.; Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks; American Chemical Society; Journal of Chemical Theory and Computation; 12; 8; 22-8-2016; 3593-3602
1549-9618
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jctc.6b00360
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.6b00360
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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