Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair

Focusing on the interesting new concept of all-metal electride, centrosymmetric molecules e^− + M^(2+) (Ni@Pb_12)^(2−) M^(2+) + e^− (M = Be, Mg, and Ca) with two anionic excess electrons located at the opposite ends of the molecule are obtained theoretically. These novel molecular all-metal electrid...

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Autores: He, Hui-Min, Li, Ying, Yang, Hui, Yu, Dan, Li, Si-Yi, Wu, Di, Hou, Jian-Hua, Zhong, Rong-Lin, Zhou, Zhong-Jun, Gu, Feng-Long, Luis Luis, Josep Maria, Li, Zhi-Ru
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
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:10256/16595
Acceso en línea:http://hdl.handle.net/10256/16595
Access Level:acceso abierto
Palabra clave:Isomeria
Isomerism
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spelling Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone PairHe, Hui-MinLi, YingYang, HuiYu, DanLi, Si-YiWu, DiHou, Jian-HuaZhong, Rong-LinZhou, Zhong-JunGu, Feng-LongLuis Luis, Josep MariaLi, Zhi-RuIsomeriaIsomerismFocusing on the interesting new concept of all-metal electride, centrosymmetric molecules e^− + M^(2+) (Ni@Pb_12)^(2−) M^(2+) + e^− (M = Be, Mg, and Ca) with two anionic excess electrons located at the opposite ends of the molecule are obtained theoretically. These novel molecular all-metal electrides can act as infrared (IR) nonlinear optical (NLO) switches. Whereas the external electric field (F) hardly changes the molecular structure of the all-metal electrides, it seriously deforms their excess electron orbitals and average static first hyperpolarizabilities (β0 e (F)). For e^− + Ca^(2+) (Ni@Pb_12)^(2−) Ca^(2+) + e^−, a small external electric field F = 8 × 10−4 au (0.04 V/Å) drives a long-range excess electron transfer from one end of the molecule through the middle all-metal anion cage (Ni@Pb_12)^(2−) to the other end. This long-range electron transfer is shown by a prominent change of excess electron orbital from double lobes to single lobe, which forms an excess electron lone pair and electronic structure Ca^(2+) (Ni@Pb_12)^(2−) Ca^(2+) + 2e^−. Therefore, the small external electric field induces a dramatic β_0 e (F) contrast from 0 (off form) to 2.2 × 106 au (on form) in allmetal electride molecule Ca(Ni@Pb_12)Ca. Obviously, such switching is high sensitive. Interestingly, in the switching process, such long-range excess electron transfer does not alter the valence and chemical bond nature. Then, this switching mechanism is a distinct nonbonding evolution named electronic structure isomerization, which means that such switching has the advantages of being fast and reversible. Besides, these all-metal electride molecules also have a rare IR transparent characteristic (1.5−10 μm) in NLO electride molecules, and hence are commendable molecular IR NLO switches. Therefore, this work opens a new research field of electric field manipulated IR NLO switches of molecular all-metal electridesThis study was supported by the National Natural Science Foundation of China (Grant Nos. 21573089, 21303066, 21173095, 21403083, 21603082, 21403075, 21673085), the State Key Development Program for Basic Research of China (Grant No. 2013CB834801), the Graduate Innovation Fund of Jilin University (Grant No. 2016158), the Spanish Ministerio de Economıa y competividad (MINECO, CTQ2014-52525-P) and the Generalitat de Catalunya (project number 2014SGR931)American Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewed11 p.application/pdfhttp://hdl.handle.net/10256/16595http://hdl.handle.net/10256/16595© Journal of Physical Chemistry C, 2017, vol. 121, núm. 1, p. 958-968Articles publicats (D-Q)He, Hui-Min Li, Ying Yang, Hui Yu, Dan Li, Si-Yi Wu, Di Hou, Jian-Hua Zhong, Rong-Lin Zhou, Zhong-Jun Gu, Feng-Long Luis Luis, Josep Maria Li, Zhi-Ru 2017 Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair Journal of Physical Chemistry C 121 1 958 968reponame: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/acs.jpcc.6b11919info:eu-repo/semantics/altIdentifier/issn/1932-7447info:eu-repo/semantics/altIdentifier/eissn/1932-7455info:eu-repo/grantAgreement/MINECO//CTQ2014-52525-PTots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/165952026-05-29T05:05:01Z
dc.title.none.fl_str_mv Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
title Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
spellingShingle Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
He, Hui-Min
Isomeria
Isomerism
title_short Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
title_full Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
title_fullStr Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
title_full_unstemmed Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
title_sort Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair
dc.creator.none.fl_str_mv He, Hui-Min
Li, Ying
Yang, Hui
Yu, Dan
Li, Si-Yi
Wu, Di
Hou, Jian-Hua
Zhong, Rong-Lin
Zhou, Zhong-Jun
Gu, Feng-Long
Luis Luis, Josep Maria
Li, Zhi-Ru
author He, Hui-Min
author_facet He, Hui-Min
Li, Ying
Yang, Hui
Yu, Dan
Li, Si-Yi
Wu, Di
Hou, Jian-Hua
Zhong, Rong-Lin
Zhou, Zhong-Jun
Gu, Feng-Long
Luis Luis, Josep Maria
Li, Zhi-Ru
author_role author
author2 Li, Ying
Yang, Hui
Yu, Dan
Li, Si-Yi
Wu, Di
Hou, Jian-Hua
Zhong, Rong-Lin
Zhou, Zhong-Jun
Gu, Feng-Long
Luis Luis, Josep Maria
Li, Zhi-Ru
author2_role author
author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Isomeria
Isomerism
topic Isomeria
Isomerism
description Focusing on the interesting new concept of all-metal electride, centrosymmetric molecules e^− + M^(2+) (Ni@Pb_12)^(2−) M^(2+) + e^− (M = Be, Mg, and Ca) with two anionic excess electrons located at the opposite ends of the molecule are obtained theoretically. These novel molecular all-metal electrides can act as infrared (IR) nonlinear optical (NLO) switches. Whereas the external electric field (F) hardly changes the molecular structure of the all-metal electrides, it seriously deforms their excess electron orbitals and average static first hyperpolarizabilities (β0 e (F)). For e^− + Ca^(2+) (Ni@Pb_12)^(2−) Ca^(2+) + e^−, a small external electric field F = 8 × 10−4 au (0.04 V/Å) drives a long-range excess electron transfer from one end of the molecule through the middle all-metal anion cage (Ni@Pb_12)^(2−) to the other end. This long-range electron transfer is shown by a prominent change of excess electron orbital from double lobes to single lobe, which forms an excess electron lone pair and electronic structure Ca^(2+) (Ni@Pb_12)^(2−) Ca^(2+) + 2e^−. Therefore, the small external electric field induces a dramatic β_0 e (F) contrast from 0 (off form) to 2.2 × 106 au (on form) in allmetal electride molecule Ca(Ni@Pb_12)Ca. Obviously, such switching is high sensitive. Interestingly, in the switching process, such long-range excess electron transfer does not alter the valence and chemical bond nature. Then, this switching mechanism is a distinct nonbonding evolution named electronic structure isomerization, which means that such switching has the advantages of being fast and reversible. Besides, these all-metal electride molecules also have a rare IR transparent characteristic (1.5−10 μm) in NLO electride molecules, and hence are commendable molecular IR NLO switches. Therefore, this work opens a new research field of electric field manipulated IR NLO switches of molecular all-metal electrides
publishDate 2017
dc.date.none.fl_str_mv 2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
peer-reviewed
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/16595
http://hdl.handle.net/10256/16595
url http://hdl.handle.net/10256/16595
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/acs.jpcc.6b11919
info:eu-repo/semantics/altIdentifier/issn/1932-7447
info:eu-repo/semantics/altIdentifier/eissn/1932-7455
info:eu-repo/grantAgreement/MINECO//CTQ2014-52525-P
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 11 p.
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 Physical Chemistry C, 2017, vol. 121, núm. 1, p. 958-968
Articles publicats (D-Q)
He, Hui-Min Li, Ying Yang, Hui Yu, Dan Li, Si-Yi Wu, Di Hou, Jian-Hua Zhong, Rong-Lin Zhou, Zhong-Jun Gu, Feng-Long Luis Luis, Josep Maria Li, Zhi-Ru 2017 Efficient External Electric Field Manipulated Nonlinear Optical Switches of All-Metal Electride Molecules with Infrared transparency: Nonbonding Electron Transfer Forms an Excess Electron Lone Pair Journal of Physical Chemistry C 121 1 958 968
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 15,811543

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