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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/54163
Ver los metadatos del registro completo
id |
CONICETDig_2d833036b4a86f96de0427bc434168c4 |
---|---|
oai_identifier_str |
oai:ri.conicet.gov.ar:11336/54163 |
network_acronym_str |
CONICETDig |
repository_id_str |
3498 |
network_name_str |
CONICET Digital (CONICET) |
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 |
_version_ |
1844613209180340224 |
score |
13.070432 |