Structure Dependence of Hyperpolarizability in Octopolar Molecules
Autor(a) principal: | |
---|---|
Data de Publicação: | 2009 |
Outros Autores: | , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/10521 https://doi.org/10.1021/ct800464t |
Resumo: | Recent Hyper Rayleigh Scattering measurements report a significant increase of second-order hyperpolarizability upon introduction of positive charges at the pyridyl end groups in trispyridyl octopolar chromophores. We calculated the geometries, linear response, and first-order hyperpolarizabilities of a series of six trispyridyl molecules both in the neutral and protonated forms. The calculations were performed with ab initio and semiempirical methods. The results are in good agreement with the experimental values and a correlation between the first hyperpolarizability and two structural properties, the N−C bond elongation and the C−C bond length alternation, Δr was established. To test these effects we computed the hyperpolarizability for several constrained geometries and confirmed the importance of planarity on the hyperpolarizability values. However the Δr values alone seem to have little influence both on the hyperpolarizability and on the gap values. Replacing the triple C≡C bond by a double C=C bond in the conjugation bridge has no significant effect due to the strong hyperpolarizability dependence on the pyridyl-benzene dihedral angle. |
id |
RCAP_8797230d737613a07583d2aecd400447 |
---|---|
oai_identifier_str |
oai:estudogeral.uc.pt:10316/10521 |
network_acronym_str |
RCAP |
network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository_id_str |
7160 |
spelling |
Structure Dependence of Hyperpolarizability in Octopolar MoleculesRecent Hyper Rayleigh Scattering measurements report a significant increase of second-order hyperpolarizability upon introduction of positive charges at the pyridyl end groups in trispyridyl octopolar chromophores. We calculated the geometries, linear response, and first-order hyperpolarizabilities of a series of six trispyridyl molecules both in the neutral and protonated forms. The calculations were performed with ab initio and semiempirical methods. The results are in good agreement with the experimental values and a correlation between the first hyperpolarizability and two structural properties, the N−C bond elongation and the C−C bond length alternation, Δr was established. To test these effects we computed the hyperpolarizability for several constrained geometries and confirmed the importance of planarity on the hyperpolarizability values. However the Δr values alone seem to have little influence both on the hyperpolarizability and on the gap values. Replacing the triple C≡C bond by a double C=C bond in the conjugation bridge has no significant effect due to the strong hyperpolarizability dependence on the pyridyl-benzene dihedral angle.American Chemical Society2009-04-14info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/10521http://hdl.handle.net/10316/10521https://doi.org/10.1021/ct800464tengJournal of Chemical Theory and Computation. 5:4 (2009) 850-8581549-9618Cardoso, C.Abreu, P. E.Nogueira, F.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2020-05-25T13:15:37Zoai:estudogeral.uc.pt:10316/10521Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:29.891670Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Structure Dependence of Hyperpolarizability in Octopolar Molecules |
title |
Structure Dependence of Hyperpolarizability in Octopolar Molecules |
spellingShingle |
Structure Dependence of Hyperpolarizability in Octopolar Molecules Cardoso, C. |
title_short |
Structure Dependence of Hyperpolarizability in Octopolar Molecules |
title_full |
Structure Dependence of Hyperpolarizability in Octopolar Molecules |
title_fullStr |
Structure Dependence of Hyperpolarizability in Octopolar Molecules |
title_full_unstemmed |
Structure Dependence of Hyperpolarizability in Octopolar Molecules |
title_sort |
Structure Dependence of Hyperpolarizability in Octopolar Molecules |
author |
Cardoso, C. |
author_facet |
Cardoso, C. Abreu, P. E. Nogueira, F. |
author_role |
author |
author2 |
Abreu, P. E. Nogueira, F. |
author2_role |
author author |
dc.contributor.author.fl_str_mv |
Cardoso, C. Abreu, P. E. Nogueira, F. |
description |
Recent Hyper Rayleigh Scattering measurements report a significant increase of second-order hyperpolarizability upon introduction of positive charges at the pyridyl end groups in trispyridyl octopolar chromophores. We calculated the geometries, linear response, and first-order hyperpolarizabilities of a series of six trispyridyl molecules both in the neutral and protonated forms. The calculations were performed with ab initio and semiempirical methods. The results are in good agreement with the experimental values and a correlation between the first hyperpolarizability and two structural properties, the N−C bond elongation and the C−C bond length alternation, Δr was established. To test these effects we computed the hyperpolarizability for several constrained geometries and confirmed the importance of planarity on the hyperpolarizability values. However the Δr values alone seem to have little influence both on the hyperpolarizability and on the gap values. Replacing the triple C≡C bond by a double C=C bond in the conjugation bridge has no significant effect due to the strong hyperpolarizability dependence on the pyridyl-benzene dihedral angle. |
publishDate |
2009 |
dc.date.none.fl_str_mv |
2009-04-14 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10316/10521 http://hdl.handle.net/10316/10521 https://doi.org/10.1021/ct800464t |
url |
http://hdl.handle.net/10316/10521 https://doi.org/10.1021/ct800464t |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Journal of Chemical Theory and Computation. 5:4 (2009) 850-858 1549-9618 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
|
_version_ |
1799133906359812096 |