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 language | English |
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Pages (from-to) | 2158-2162 |
Number of pages | 5 |
Journal | Journal of Physical Chemistry Letters |
Volume | 6 |
Issue number | 12 |
DOIs | |
State | Published - Jun 18 2015 |
Bibliographical note
Publisher Copyright:© 2015 American Chemical Society.
Keywords
- bond length alternation
- bond order alternation
- cyanines/polymethines
- nonlinear optics
ASJC Scopus subject areas
- General Materials Science
- Physical and Theoretical Chemistry