Saturation of cubic optical nonlinearity in long-chain polyene oligomers.

The scaling of the cubic nonlinearity gamma with chain length in polyenic molecules has received considerable theoretical attention. Earlier experimental investigations have been restricted to oligomers with fewer than 20 double bonds because of problems associated with the synthesis and solubility of conjugated molecules. These synthetic difficulties have been overcome in the present study by the use of modern living polymerization techniques. Solution measurements of gamma as a function of chain length in long-chain (up to 240 double bonds) model polyene oligomers are reported. A saturation of the increase of gamma with chain length is observed, and the onset of this saturation occurs for chain lengths considerably longer than predicted from theory.