Date

2013

Document Type

Dissertation

Degree

Doctor of Philosophy

Department

Physics

First Adviser

Biaggio, Ivan

Other advisers/committee members

Stavola, Michael; Rotkin, Slava; Bartoli, Filbert; Ferguson, Gregory

Abstract

The determination of the wavelength dependence of the complex third-order polarizability of organic molecules delivers information on the mechanisms of resonance enhancement and allows for comparison of the two-photon absorption cross sections on their peak to the off-resonant third-order polarizabilities. The experimental technique of degenerate four-wave mixing offers several advantages over other comparable techniques, including sensitivity, background-free signal, automatization, and information on excited state lifetimes. This work uses experimental data, computational chemistry, and analysis of the relevant terms in the sum-over-states quantum mechanics expression to analyze the significant contributions to the third-order polarizability, mechanisms of resonance enhancement, and comparison of the off resonant values, to peak resonant values. This information provides insight to the structure-property relationships for the third-order polarizability, allows for comparison to fundamental limits, and assessment of the potential for molecules to form solid state materials with a large third-order susceptibility.The use of donor-acceptor (D/A) substitution allows for the realization of small molecules with large third-order polarizabilities. However, in contrast to symmetric non-D/A oligomers that have third-order polarizabilities which scale by a power law as the molecule is made larger, D/A substituted molecules only scale up to a certain length, beyond which the molecule is over-extended and the third-order polarizability does not increase further. This work will analyze the scaling of non-D/A and D/A substituted molecules, determine the optimum length for D/A substituted molecules, and explain the physics of the saturation.

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