Electronic and vibrational nonlinear optical properties of five representative electrides

The electrides have a very special electronic structure with diffuse excess electrons not localized on any specific atom. Such systems are known to have huge electronic nonlinear optical (NLO) properties. Here, we determine and analyze the vibrational, as compared to the electronic, NLO properties f...

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Autores: Garcia Borràs, Marc, Solà i Puig, Miquel, Luis Luis, Josep Maria, Kirtman, Bernard
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2012
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:10256/11404
Acceso en línea:http://hdl.handle.net/10256/11404
Access Level:acceso embargado
Palabra clave:Anions
Electrons
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spelling Electronic and vibrational nonlinear optical properties of five representative electridesGarcia Borràs, MarcSolà i Puig, MiquelLuis Luis, Josep MariaKirtman, BernardAnionsElectronsThe electrides have a very special electronic structure with diffuse excess electrons not localized on any specific atom. Such systems are known to have huge electronic nonlinear optical (NLO) properties. Here, we determine and analyze the vibrational, as compared to the electronic, NLO properties for a representative set of electrides: Li@Calix, Na@Calix, Li@B 10H 14, Li 2 ·TCNQ ·-, and Na 2 ·TCNQ ·-. The static and dynamic vibrational (hyper)polarizabilities are computed by the nuclear relaxation method (with field-induced coordinates and the infinite optical frequency approximation) at the UB3LYP level using a hybrid Pople basis set. In general, the static vibrational β vec and γ ∥ exceed the corresponding static electronic property values by up to an order of magnitude. The same comparison for dynamic vibrational hyperpolarizabilities shows a smaller ratio. For the intensity-dependent refractive index (IDRI) and dc-Kerr processes, the ratio is on the order of unity or somewhat larger; it is less for the dc-Pockels and the electric field induced second harmonic (EFISH) effects (as well as the static α̂) but still important. The role of anharmonicity, motion of the alkali atoms, and substitution of Na for Li is discussed along with specific aspects of the charge distribution associated with the excess electronThe following organizations are thanked for financial support: the Spanish Ministerio de Ciencia e Innovacion (MICINN, CTQ2011-23156/BQU) and the DIUE of the Generalitat de Catalunya (2009SGR637). M.G.-B. thanks the Spanish MEC for a doctoral fellowship, no. AP2010-2517. Support for the research of M.S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya. Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was provided by grant UNGI08-4E-003American Chemical Society (ACS)Ministerio de Ciencia e Innovación (Espanya)Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recercainfoinfo2012info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/11404http://hdl.handle.net/10256/11404© Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 8, p. 2688-2697Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/ct300433qinfo:eu-repo/semantics/altIdentifier/issn/1549-9618info:eu-repo/semantics/altIdentifier/eissn/1549-9626info:eu-repo/grantAgreement/MICINN//CTQ2011-23156AGAUR/2009-2014/2009 SGR-637Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/114042026-05-29T05:05:01Z
dc.title.none.fl_str_mv Electronic and vibrational nonlinear optical properties of five representative electrides
title Electronic and vibrational nonlinear optical properties of five representative electrides
spellingShingle Electronic and vibrational nonlinear optical properties of five representative electrides
Garcia Borràs, Marc
Anions
Electrons
title_short Electronic and vibrational nonlinear optical properties of five representative electrides
title_full Electronic and vibrational nonlinear optical properties of five representative electrides
title_fullStr Electronic and vibrational nonlinear optical properties of five representative electrides
title_full_unstemmed Electronic and vibrational nonlinear optical properties of five representative electrides
title_sort Electronic and vibrational nonlinear optical properties of five representative electrides
dc.creator.none.fl_str_mv Garcia Borràs, Marc
Solà i Puig, Miquel
Luis Luis, Josep Maria
Kirtman, Bernard
author Garcia Borràs, Marc
author_facet Garcia Borràs, Marc
Solà i Puig, Miquel
Luis Luis, Josep Maria
Kirtman, Bernard
author_role author
author2 Solà i Puig, Miquel
Luis Luis, Josep Maria
Kirtman, Bernard
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca
dc.subject.none.fl_str_mv Anions
Electrons
topic Anions
Electrons
description The electrides have a very special electronic structure with diffuse excess electrons not localized on any specific atom. Such systems are known to have huge electronic nonlinear optical (NLO) properties. Here, we determine and analyze the vibrational, as compared to the electronic, NLO properties for a representative set of electrides: Li@Calix, Na@Calix, Li@B 10H 14, Li 2 ·TCNQ ·-, and Na 2 ·TCNQ ·-. The static and dynamic vibrational (hyper)polarizabilities are computed by the nuclear relaxation method (with field-induced coordinates and the infinite optical frequency approximation) at the UB3LYP level using a hybrid Pople basis set. In general, the static vibrational β vec and γ ∥ exceed the corresponding static electronic property values by up to an order of magnitude. The same comparison for dynamic vibrational hyperpolarizabilities shows a smaller ratio. For the intensity-dependent refractive index (IDRI) and dc-Kerr processes, the ratio is on the order of unity or somewhat larger; it is less for the dc-Pockels and the electric field induced second harmonic (EFISH) effects (as well as the static α̂) but still important. The role of anharmonicity, motion of the alkali atoms, and substitution of Na for Li is discussed along with specific aspects of the charge distribution associated with the excess electron
publishDate 2012
dc.date.none.fl_str_mv 2012
info
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/11404
http://hdl.handle.net/10256/11404
url http://hdl.handle.net/10256/11404
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/ct300433q
info:eu-repo/semantics/altIdentifier/issn/1549-9618
info:eu-repo/semantics/altIdentifier/eissn/1549-9626
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv © Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 8, p. 2688-2697
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
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reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
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