Distinguishing the Effects of Bond-Length Alternation versus Bond-Order Alternation on the Nonlinear Optical Properties of π-Conjugated Chromophores

Handle URI:
http://hdl.handle.net/10754/566100
Title:
Distinguishing the Effects of Bond-Length Alternation versus Bond-Order Alternation on the Nonlinear Optical Properties of π-Conjugated Chromophores
Authors:
Gieseking, Rebecca L.; Risko, Chad; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
Understanding the relationships between the molecular nonlinear optical (NLO) properties and the bond-length alternation (BLA) or π-bond-order alternation (BOA) along the molecular backbone of linear π-conjugated systems has proven widely useful in the development of NLO organic chromophores and materials. Here, we examine model polymethines to elucidate the reliability of these relationships. While BLA is solely a measure of molecular geometric structure, BOA includes information pertaining to the electronic structure. As a result, BLA is found to be a good predictor of NLO properties only when optimized geometries are considered, whereas BOA is more broadly applicable. Proper understanding of the distinction between BLA and BOA is critical when designing computational studies of NLO properties, especially for molecules in complex environments or in nonequilibrium geometries. © 2015 American Chemical Society.
KAUST Department:
Chemical Science Program; Physical Sciences and Engineering (PSE) Division; Materials Science and Engineering Program; Solar and Photovoltaic Engineering Research Center (SPERC)
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry Letters
Issue Date:
18-Jun-2015
DOI:
10.1021/acs.jpclett.5b00812
Type:
Article
ISSN:
1948-7185
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; Materials Science and Engineering Program; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorGieseking, Rebecca L.en
dc.contributor.authorRisko, Chaden
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2015-08-12T09:28:15Zen
dc.date.available2015-08-12T09:28:15Zen
dc.date.issued2015-06-18en
dc.identifier.issn1948-7185en
dc.identifier.doi10.1021/acs.jpclett.5b00812en
dc.identifier.urihttp://hdl.handle.net/10754/566100en
dc.description.abstractUnderstanding the relationships between the molecular nonlinear optical (NLO) properties and the bond-length alternation (BLA) or π-bond-order alternation (BOA) along the molecular backbone of linear π-conjugated systems has proven widely useful in the development of NLO organic chromophores and materials. Here, we examine model polymethines to elucidate the reliability of these relationships. While BLA is solely a measure of molecular geometric structure, BOA includes information pertaining to the electronic structure. As a result, BLA is found to be a good predictor of NLO properties only when optimized geometries are considered, whereas BOA is more broadly applicable. Proper understanding of the distinction between BLA and BOA is critical when designing computational studies of NLO properties, especially for molecules in complex environments or in nonequilibrium geometries. © 2015 American Chemical Society.en
dc.publisherAmerican Chemical Society (ACS)en
dc.subjectbond length alternationen
dc.subjectbond order alternationen
dc.subjectcyanines/polymethinesen
dc.subjectnonlinear opticsen
dc.titleDistinguishing the Effects of Bond-Length Alternation versus Bond-Order Alternation on the Nonlinear Optical Properties of π-Conjugated Chromophoresen
dc.typeArticleen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentMaterials Science and Engineering Programen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalThe Journal of Physical Chemistry Lettersen
kaust.authorBredas, Jean-Lucen
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