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STUDY OF THE EXCITED-STATE ABSORPTION PROPERTIES OF POLYMETHINE MOLECULES
Title
STUDY OF THE EXCITED-STATE ABSORPTION PROPERTIES OF POLYMETHINE MOLECULES.
Creator
Lepkowicz, Richard Stanley, Van Stryland, Eric W., University of Central Florida
Abstract / Description
This dissertation investigates excited-state nonlinearities in a series of polymethine dyes for the application of nanosecond optical limiting. Optical limiters are devices that for low intensity light exhibit a high linear transmittance, but for high intensity light strongly attenuate the incident radiation. These devices would serve to protect optical sensors from intense laser radiation by clamping the maximum energy allowed through an optical system below the damage threshold of the...
Show moreThis dissertation investigates excited-state nonlinearities in a series of polymethine dyes for the application of nanosecond optical limiting. Optical limiters are devices that for low intensity light exhibit a high linear transmittance, but for high intensity light strongly attenuate the incident radiation. These devices would serve to protect optical sensors from intense laser radiation by clamping the maximum energy allowed through an optical system below the damage threshold of the sensor. The search is ongoing for optical materials that are both broadband and have high damage thresholds to be effective materials for limiting applications. Polymethine dyes are promising compounds due to a strong and broad excited-state absorption (ESA) band in the visible region. However, the effectiveness of polymethine molecules as applied to optical limiting is hindered by a saturation of the ESA process at high fluences. Experiments and theoretical modeling are performed to determine the root causes of this saturation effect in both the picosecond and nanosecond time regime. The polymethine molecules studied have chromophore lengths from di- to pentacarbocyanine (2 to 5 -CH=CH- groups) with various bridge structures. This allows us to develop relationships between the molecular parameters of the polymethine molecules and overall nonlinear absorption performance. The experiments conducted included femtosecond white light continuum pump-probe experiments to measure ESA spectra, picosecond two-color polarization-resolved pump-probe to measure excited-state dynamics and the orientation of transition dipole moments, and picosecond and nanosecond optical limiting and z-scans. From these experiments we are able to develop energy level models that describe the nonlinear absorption processes in polymethines from the picosecond to nanosecond time regime. This work, along with the quantum chemical modeling performed at the Institute of Physics and National Academy of Sciences of Ukraine, has resulted in the creation of dyes that have improved photochemical stability with larger nonlinearities. These are useful not only for optical limiting but also for a wide variety of nonlinear optical applications.
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Date Issued
2004
Identifier
CFE0000002, ucf:46115
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0000002
CHEMICAL STRUCTURE - NONLINEAR OPTICAL PROPERTY RELATIONSHIPS FOR A SERIES OF TWO-PHOTON ABSORBING FLUORENE MOLECULES
Title
CHEMICAL STRUCTURE - NONLINEAR OPTICAL PROPERTY RELATIONSHIPS FOR A SERIES OF TWO-PHOTON ABSORBING FLUORENE MOLECULES.
Creator
Hales, Joel McCajah, Van Stryland, Eric W., University of Central Florida
Abstract / Description
This dissertation reports on the investigation of two-photon absorption (2PA) in a series of fluorenyl molecules. Several current and emerging technologies exploit this optical nonlinearity including two-photon fluorescence imaging, three-dimensional microfabrication, site-specific photodynamic cancer therapy and biological caging studies. The two key features of this nonlinearity which make it an ideal candidate for the above applications are its quadratic dependence on the incident...
Show moreThis dissertation reports on the investigation of two-photon absorption (2PA) in a series of fluorenyl molecules. Several current and emerging technologies exploit this optical nonlinearity including two-photon fluorescence imaging, three-dimensional microfabrication, site-specific photodynamic cancer therapy and biological caging studies. The two key features of this nonlinearity which make it an ideal candidate for the above applications are its quadratic dependence on the incident irradiance and the improved penetration into absorbing media that it affords. As a consequence of the burgeoning field which exploits 2PA, it is a goal to find materials that exhibit strong two-photon absorbing capabilities. Organic materials are promising candidates for 2PA applications because their material properties can be tailored through molecular engineering thereby facilitating optimization of their nonlinear optical properties. Fluorene derivatives are particularly interesting since they possess high photochemical stability for organic molecules and are generally strongly fluorescent. By systematically altering the structural properties in a series of fluorenyl molecules, we have determined how these changes affect their two-photon absorbing capabilities. This was accomplished through characterization of both the strength and location of their 2PA spectra. In order to ensure the validity of these results, three separate nonlinear characterization techniques were employed: two-photon fluorescence spectroscopy, white-light continuum pump-probe spectroscopy, and the Z-scan technique. In addition, full linear spectroscopic characterization was performed on these molecules along with supplementary quantum chemical calculations to obtain certain molecular properties that might impact the nonlinearity. Different designs in chemical architecture allowed investigation of the effects of symmetry, solvism, donor-acceptor strengths, conjugation length, and multi-branched geometries on the two-photon absorbing properties of these molecules. In addition, the means to enhance 2PA via intermediate state resonances was investigated. To provide plausible explanations for the experimentally observed trends, a conceptually simple three level model was employed. The subsequent correlations found between chemical structure and the linear and nonlinear optical properties of these molecules provided definitive conclusions on how to properly optimize their two-photon absorbing capabilities. The resulting large nonlinearities found in these molecules have already shown promise in a variety of the aforementioned applications.
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Date Issued
2004
Identifier
CFE0000005, ucf:46103
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0000005