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

Rebecca L. Gieseking, Chad Risko, Jean-Luc Bredas

Research output: Contribution to journalArticlepeer-review

49 Scopus citations

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.
Original languageEnglish (US)
Pages (from-to)2158-2162
Number of pages5
JournalThe Journal of Physical Chemistry Letters
Volume6
Issue number12
DOIs
StatePublished - May 28 2015

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