Nonlinear optical properties of push-pull porphyrins and retinal derivatives: Structure-function relationship, pH and solvent effects

ORGN 351

Paresh Chandra Ray, Department of Chemistry, Department of Chemistry, Jackson State University, Jackson, MS
We present a quantum-chemical analysis of the molecular structure and first hyperpolarizabilities of a series of push-pull porphyrins and retinal derivatives. Ab initio coupled perturbed Hatree-Fock (CPHF) calculations using 6-31G** basis set have been performed to investigate the static first hyperpolarizabilities (β°) of those NLO chromophores. The effect of donor or acceptor substitution and also elongation of the conjugation path length are established to demonstrate the engineering guidelines for enhancing molecular optical non-linearities. The solvent induced effects on the NLO properties are studied by using the self-consistent reaction field (SCRF) method. Dynamic first hyperpolarizability (β) was investigated using ZINDO/Correction Vector (CV) method including solvent effects. It is found that the effect of conjugation path length and solvent polarity on β’s are different for neutral, ionic and zwitterionic molecules. Theoretical results will be compared with the experimental values wherever available in the literature and the results are evaluated in detail about the agreements and disagreements between theoretical and experimental findings.
 

Materials, Devices, and Switches
1:00 PM-5:00 PM, Tuesday, August 24, 2004 Pennsylvania Convention Center -- 201B, Oral

Division of Organic Chemistry

The 228th ACS National Meeting, in Philadelphia, PA, August 22-26, 2004