Distinguishing the effects of bond-length alternation versus bond-order alternation on the nonlinear optical properties of conjugated chromophores

Rebecca L. Gieseking, Chad Risko, Jean Luc Brédas

Research output: Contribution to journalArticlepeer-review

60 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.

Original languageEnglish (US)
Pages (from-to)2158-2162
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume6
Issue number12
DOIs
StatePublished - Jun 18 2015
Externally publishedYes

Keywords

  • bond length alternation
  • bond order alternation
  • cyanines/polymethines
  • nonlinear optics

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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