TY - JOUR
T1 - Bond Ellipticity Alternation
T2 - An Accurate Descriptor of the Nonlinear Optical Properties of π-Conjugated Chromophores
AU - Lopes, Thiago O.
AU - Machado, Daniel F.Scalabrini
AU - Risko, Chad
AU - Brédas, Jean Luc
AU - De Oliveira, Heibbe C.B.
N1 - Funding Information:
The work at University of Brasiliá was funded by Conselho Nacional de Desenvolvimento Cientifí co e Tecnológico (CNPq) and Coordenaca̧ õ de Aperfeico̧ amento Pessoal de Niveĺ Superior (CAPES). The work at the University of Kentucky was supported in part by start-up funds provided to C.R. by University of Kentucky Vice President for Research. The work at Georgia Tech was supported by the Georgia Research Alliance. We are grateful to Dr. Veaceslav Coropceanu, Dr. Rebecca Gieseking, and Dr. Valter Henrique Carvalho-Silva for stimulating discussions.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/3/15
Y1 - 2018/3/15
N2 - Well-defined structure-property relationships offer a conceptual basis to afford a priori design principles to develop novel π-conjugated molecular and polymer materials for nonlinear optical (NLO) applications. Here, we introduce the bond ellipticity alternation (BEA) as a robust parameter to assess the NLO characteristics of organic chromophores and illustrate its effectiveness in the case of streptocyanines. BEA is based on the symmetry of the electron density, a physical observable that can be determined from experimental X-ray electron densities or from quantum-chemical calculations. Through comparisons to the well-established bond-length alternation and π-bond order alternation parameters, we demonstrate the generality of BEA to foreshadow NLO characteristics and underline that, in the case of large electric fields, BEA is a more reliable descriptor. Hence, this study introduces BEA as a prominent descriptor of organic chromophores of interest for NLO applications.
AB - Well-defined structure-property relationships offer a conceptual basis to afford a priori design principles to develop novel π-conjugated molecular and polymer materials for nonlinear optical (NLO) applications. Here, we introduce the bond ellipticity alternation (BEA) as a robust parameter to assess the NLO characteristics of organic chromophores and illustrate its effectiveness in the case of streptocyanines. BEA is based on the symmetry of the electron density, a physical observable that can be determined from experimental X-ray electron densities or from quantum-chemical calculations. Through comparisons to the well-established bond-length alternation and π-bond order alternation parameters, we demonstrate the generality of BEA to foreshadow NLO characteristics and underline that, in the case of large electric fields, BEA is a more reliable descriptor. Hence, this study introduces BEA as a prominent descriptor of organic chromophores of interest for NLO applications.
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U2 - 10.1021/acs.jpclett.8b00478
DO - 10.1021/acs.jpclett.8b00478
M3 - Article
C2 - 29498530
AN - SCOPUS:85043992232
SN - 1948-7185
VL - 9
SP - 1377
EP - 1383
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 6
ER -