Nonlinear Optical Properties of XPh4 (X = B-, C, N+, P+): A New Class of Molecules with a Negative Third-Order Polarizability

Handle URI:
http://hdl.handle.net/10754/558585
Title:
Nonlinear Optical Properties of XPh4 (X = B-, C, N+, P+): A New Class of Molecules with a Negative Third-Order Polarizability
Authors:
Gieseking, Rebecca L.; Ensley, Trenton R.; Hu, Honghua; Hagan, David J.; Risko, Chad; Van Stryland, Eric W.; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
Organic π-conjugated materials have been widely used for a variety of nonlinear optical (NLO) applications. Molecules with negative real components Re(γ) of the third-order polarizability, which leads to nonlinear refraction in macroscopic systems, have important benefits for several NLO applications. However, few organic systems studied to date have negative Re(γ) in the long wavelength limit, and all inorganic materials show positive nonlinear refraction in this limit. Here, we introduce a new class of molecules of the form X(C6H5)4, where X = B-, C, N+, and P+, that have negative Re(γ). The molecular mechanism for the NLO properties in these systems is very different from those in typical linear conjugated systems: these systems have a band of excited states involving single-electron excitations within the π-system, several of which have significant coupling to the ground state. Thus, Re(γ) cannot be understood in terms of a simplified essential-state model and must be analyzed in the context of the full sum-over-states expression. Although Re(γ) is significantly smaller than that of other commonly-studied NLO chromophores, the introduction of a new molecular architecture offering the potential for a negative Re(γ) introduces new avenues of molecular design for NLO applications.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)
Citation:
Nonlinear Optical Properties of XPh4 (X = B-, C, N+, P+): A New Class of Molecules with a Negative Third-Order Polarizability 2015:150622124820007 Journal of the American Chemical Society
Journal:
Journal of the American Chemical Society
Issue Date:
22-Jun-2015
DOI:
10.1021/jacs.5b04377
Type:
Article
ISSN:
0002-7863; 1520-5126
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.5b04377
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorGieseking, Rebecca L.en
dc.contributor.authorEnsley, Trenton R.en
dc.contributor.authorHu, Honghuaen
dc.contributor.authorHagan, David J.en
dc.contributor.authorRisko, Chaden
dc.contributor.authorVan Stryland, Eric W.en
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2015-06-28T13:38:48Zen
dc.date.available2015-06-28T13:38:48Zen
dc.date.issued2015-06-22en
dc.identifier.citationNonlinear Optical Properties of XPh4 (X = B-, C, N+, P+): A New Class of Molecules with a Negative Third-Order Polarizability 2015:150622124820007 Journal of the American Chemical Societyen
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.5b04377en
dc.identifier.urihttp://hdl.handle.net/10754/558585en
dc.description.abstractOrganic π-conjugated materials have been widely used for a variety of nonlinear optical (NLO) applications. Molecules with negative real components Re(γ) of the third-order polarizability, which leads to nonlinear refraction in macroscopic systems, have important benefits for several NLO applications. However, few organic systems studied to date have negative Re(γ) in the long wavelength limit, and all inorganic materials show positive nonlinear refraction in this limit. Here, we introduce a new class of molecules of the form X(C6H5)4, where X = B-, C, N+, and P+, that have negative Re(γ). The molecular mechanism for the NLO properties in these systems is very different from those in typical linear conjugated systems: these systems have a band of excited states involving single-electron excitations within the π-system, several of which have significant coupling to the ground state. Thus, Re(γ) cannot be understood in terms of a simplified essential-state model and must be analyzed in the context of the full sum-over-states expression. Although Re(γ) is significantly smaller than that of other commonly-studied NLO chromophores, the introduction of a new molecular architecture offering the potential for a negative Re(γ) introduces new avenues of molecular design for NLO applications.en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.5b04377en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.5b04377.en
dc.titleNonlinear Optical Properties of XPh4 (X = B-, C, N+, P+): A New Class of Molecules with a Negative Third-Order Polarizabilityen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionSchool of Chemistry and Biochemistry and Center for Organic Photonics and Electronics Georgia Institute of Technology Atlanta, Georgia 30332"0400, USAen
dc.contributor.institutionCREOL, The College of Optics and Photonics University of Central Florida Orlando, Florida 32816, USAen
dc.contributor.institutionDepartment of Chemistry and Center for Applied Energy Research University of Kentucky Lexington, Kentucky 40506"0055, USAen
kaust.authorBredas, Jean-Lucen
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