The main goal of this dissertation is to investigate the third-order nonlinearity of organic molecules. This topic contains two aspects: two-photon absorption (2PA) and nonlinear refraction (NLR), which are associated with the imaginary and real part of the third-order nonlinearity (χ (3)) of the material, respectively. With the optical properties tailored through meticulous molecular structure engineering, organic molecules are promising candidates to exhibit large third-order nonlinearities. Both linear (absorption, fluorescence, fluorescence excitation anisotropy) and nonlinear (Z-scan, two-photon fluorescence, pump-probe) techniques are described and utilized to fully characterize the spectroscopic properties of organic molecules in solution or solid-state form. These properties are then analyzed by quantum chemical calculations or other specific quantum mechanical model to understand the origins of the nonlinearities as well as the correlations with their unique molecular structural features. These calculations are performed by collaborators. The 2PA study of organic materials is focused on the structure-2PA property relationships of four groups of dyes with specific molecular design approaches as the following: (1) Acceptor-π-Acceptor dyes for large 2PA cross section, (2) Donor-π-Acceptor dyes for strong solvatochromic effects upon the 2PA spectra, (3) Near-infrared polymethine dyes for a symmetry breaking effect, (4) Sulfur-squaraines vs. oxygen-squaraines to study the role of sulfur atom replacement upon their 2PA spectra. Additionally, the 2PA spectrum of a solid-state single crystal made from a Donor-π-Acceptor dye is measured, and the anisotropic nonlinearity is studied with respect to different incident polarizations. These studies further advance our iv understanding towards an ultimate goal to a predictive capability for the 2PA properties of organic molecules. The NLR study on molecules is focused on the temporal and spectral dispersion of the nonlinear refraction index, n2, of the molecules. Complicated physical mechanisms, originating from either electronic transitions or nuclei movement, are introduced in general. By adopting a prism compressor / stretcher to control the pulsewidth, an evolution of n2 with respect to incident pulsewidth is measured on a simple inorganic molecule –carbon disulfide (CS2) in neat liquid at 700 nm and 1064 nm to demonstrate the pulsewidth dependent nonlinear refraction. The n2 spectra of CS2 and certain organic molecules are measured by femtosecond pulses, which are then analyzed by a 3-level model, a simplified "Sum-over-states" quantum mechanical model. These studies can serve as a precursor for future NLR investigations.
| Identifer | oai:union.ndltd.org:ucf.edu/oai:stars.library.ucf.edu:etd-3206 |
| Date | 01 January 2012 |
| Creators | Hu, Honghua |
| Publisher | STARS |
| Source Sets | University of Central Florida |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | Electronic Theses and Dissertations |
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