Current Search: Nonlinear absorption (x)
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- Title
- NONLINEAR ABSORPTION AND FREE CARRIER RECOMBINATION IN DIRECT GAP SEMICONDUCTORS.
- Creator
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Olszak, Peter, Van Stryland, Eric, University of Central Florida
- Abstract / Description
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Nonlinear absorption of Indium Antimonide (InSb) has been studied for many years, yet due to the complexity of absorption mechanisms and experimental difficulties in the infrared, this is still a subject of research. Although measurements have been made in the past, a consistent model that worked for both picosecond and nanosecond pulse widths had not been demonstrated. In this project, temperature dependent two-photon (2PA) and free carrier absorption (FCA) spectra of InSb are measured using...
Show moreNonlinear absorption of Indium Antimonide (InSb) has been studied for many years, yet due to the complexity of absorption mechanisms and experimental difficulties in the infrared, this is still a subject of research. Although measurements have been made in the past, a consistent model that worked for both picosecond and nanosecond pulse widths had not been demonstrated. In this project, temperature dependent two-photon (2PA) and free carrier absorption (FCA) spectra of InSb are measured using femtosecond, picosecond, and nanosecond IR sources. The 2PA spectrum is measured at room temperature with femtosecond pulses, and the temperature dependence of 2PA and FCA is measured at 10.6m using a nanosecond CO2 laser giving results consistent with the temperature dependent measurements at several wavelengths made with a tunable picosecond system. Measurements over this substantial range of pulse widths give results for FCA and 2PA consistent with a recent theoretical model for FCA. While the FCA cross section has been generally accepted in the past to be a constant for the temperatures and wavelengths used in this study, this model predicts that it varies significantly with temperature as well as wavelength. Additionally, the results for 2PA are consistent with the band gap scaling (Eg-3) predicted by a simple two parabolic band model. Using nanosecond pulses from a CO2 laser enables the recombination rates to be determined through nonlinear transmittance measurements. Three-photon absorption is also observed in InSb for photon energies below the 2PA band edge. Prior to this work, data on three-photon absorption (3PA) in semiconductors was scarce and most experiments were performed over narrow spectral ranges, making comparison to the available theoretical models difficult. There was also disagreement between the theoretical results generated by different models, primarily in the spectral behavior. Therefore, we studied the band gap scaling and spectra of 3PA in several semiconductors by the Z-scan technique. The 3PA coefficient is found to vary as (Eg-7), as predicted by the scaling rules of simple two parabolic band models. The spectral behavior, which is considerably more complex than for 2PA, is found to agree well with a recently published theory based on a four-band model.
Show less - Date Issued
- 2010
- Identifier
- CFE0003402, ucf:48418
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003402
- Title
- EXPERIMENTAL AND THEORETICAL APPROACHES TO CHARACTERIZATION OF ELECTRONIC NONLINEARITIES IN DIRECT-GAP SEMICONDUCTORS.
- Creator
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Cirloganu, Claudiu, Van Stryland, Eric, University of Central Florida
- Abstract / Description
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The general goal of this dissertation is to provide a comprehensive description of the limitations of established theories on bound electronic nonlinearities in direct-gap semiconductors by performing various experiments on wide and narrow bandgap semiconductors along with developing theoretical models. Nondegenerate two-photon absorption (2PA) is studied in several semiconductors showing orders of magnitude enhancement over the degenerate counterpart. In addition, three-photon absorption ...
Show moreThe general goal of this dissertation is to provide a comprehensive description of the limitations of established theories on bound electronic nonlinearities in direct-gap semiconductors by performing various experiments on wide and narrow bandgap semiconductors along with developing theoretical models. Nondegenerate two-photon absorption (2PA) is studied in several semiconductors showing orders of magnitude enhancement over the degenerate counterpart. In addition, three-photon absorption (3PA) is studied in ZnSe and other semiconductors and a new theory using a Kane 4-band model is developed which fits new data well. Finally, the narrow gap semiconductor InSb is studied with regard to multiphoton absorption, free-carrier nonlinearities and decay mechanisms. The non-degenerate two-photon absorption was investigated in several direct-gap semiconductors with picosecond and femtosecond pulses. Large enhancements in 2PA were demonstrated when employing highly non-degenerate photon pairs and the results were shown to be consistent to a simple 2-parabolic band theory based on a ÃÂ"dressedÃÂ" state approach. The nonlinear refractive index induced in such configurations was also calculated and possible implications of such extreme behavior are discussed. A large number of measurements of 3PA were taken at multiple wavelengths and in several semiconductors. The subsequent analysis has shown that simple 2-band model calculations (based on either perturbative or tunneling approaches) do not adequately describe the experimental trends. A more comprehensive model, based on KaneÃÂ's 4-band theory was developed and we calculate three-photon spectra for zincblende structures within the perturbative framework. We have confirmed the results of our calculations performing a series of Z-scans in semiconductors ZnSe and ZnS, yielding complete experimental three-photon spectra. A systematic approach based on using a large variety of pulse durations was needed to quantify the wealth of nonlinear optical processes in InSb, accessible in the mid-infrared range. Femtosecond pulses provided a lower limit to measurements of the instantaneous effects (absorptive and refractive), while picosecond pulses allowed further characterization of the free-carrier effects, including population dynamics in the high density regime (Auger effects). The model developed permitted us to verify the temperature dependence of free-carrier absorption recently predicted, and to successfully model optical limiting data with longer, nanosecond pulses.
Show less - Date Issued
- 2010
- Identifier
- CFE0003401, ucf:48417
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003401
- Title
- STUDY OF THE EXCITED-STATE ABSORPTION PROPERTIES OF POLYMETHINE MOLECULES.
- Creator
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Lepkowicz, Richard Stanley, Van Stryland, Eric W., University of Central Florida
- Abstract / Description
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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.
Show less - Date Issued
- 2004
- Identifier
- CFE0000002, ucf:46115
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000002
- Title
- MOLECULAR STRUCTURE NONLINEAR OPTICAL PROPERTY RELATIONSHIPS FOR A SERIES OF POLYMETHINE AND SQUARAINE MOLECULES.
- Creator
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Fu, Jie, Van Stryland, Eric, University of Central Florida
- Abstract / Description
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This dissertation reports on the investigation of the relationships between molecular structure and two-photon absorption (2PA) properties for a series of polymethine and squaraine molecules. Current and emerging applications exploiting the quadratic dependence upon laser intensity, such as two-photon fluorescence imaging, three-dimensional microfabrication, optical data storage and optical limiting, have motivated researchers to find novel materials exhibiting strong 2PA. Organic materials...
Show moreThis dissertation reports on the investigation of the relationships between molecular structure and two-photon absorption (2PA) properties for a series of polymethine and squaraine molecules. Current and emerging applications exploiting the quadratic dependence upon laser intensity, such as two-photon fluorescence imaging, three-dimensional microfabrication, optical data storage and optical limiting, have motivated researchers to find novel materials exhibiting strong 2PA. Organic materials are promising candidates because their linear and nonlinear optical properties can be optimized for applications by changing their structures through molecular engineering. Polymethine and squaraine dyes are particularly interesting because they are fluorescent and showing large 2PA. We used three independent nonlinear spectroscopic techniques (Z-scan, two-photon fluorescence and white-light continuum pump-probe spectroscopy) to obtain the 2PA spectra revealing 2PA bands, and we confirm the experimental data by comparing the results from the different methods mentioned. By systematically altering the structure of polyemthines and squaraines, we studied the effects of molecular symmetry, strength of donor terminal groups, conjugation length of the chromophore chain, polarity of solvents, and the effects of placing bridge molecules inside the chromophore chain on the 2PA properties. We also compared polymethine, squaraine, croconium and tetraon dyes with the same terminal groups to study the effects of the different additions inserted within the chromophore chain on their optical properties. Near IR absorbing squaraine dyes were experimentally observed to show extremely large 2PA cross sections ( 30000GM). A simplified three-level model was used to fit the measured 2PA spectra and detailed quantum chemical calculations revealed the reasons for the squaraine to exhibit strong 2PA. In addition, two-photon excitation fluorescence anisotropy spectra were measured through multiple 2PA transitions. A theoretical model based on four-levels with two intermediate states was derived and used for analysis of the experimental data.
Show less - Date Issued
- 2006
- Identifier
- CFE0001350, ucf:46967
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001350
- Title
- Two-photon absorption in bulk semiconductors and quantum well structures and its applications.
- Creator
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Pattanaik, Himansu, Vanstryland, Eric, Hagan, David, Delfyett, Peter, Schoenfeld, Winston, Peale, Robert, University of Central Florida
- Abstract / Description
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The purpose of this dissertation is to provide a study and possible applications of two-photon absorption (2PA), in direct-gap semiconductors and quantum-well (QW) semiconductor structures. One application uses extremely nondegenerate (END) 2PA, for mid-infrared (mid-IR) detection in uncooled semiconductors. The use of END, where the two photons have very different energies gives strong enhancement comapared to degenerate 2PA. This END-2PA enhanced detection is also applied to mid-IR imaging...
Show moreThe purpose of this dissertation is to provide a study and possible applications of two-photon absorption (2PA), in direct-gap semiconductors and quantum-well (QW) semiconductor structures. One application uses extremely nondegenerate (END) 2PA, for mid-infrared (mid-IR) detection in uncooled semiconductors. The use of END, where the two photons have very different energies gives strong enhancement comapared to degenerate 2PA. This END-2PA enhanced detection is also applied to mid-IR imaging and light detection and ranging (LIDAR) in uncooled direct-gap photodiodes. A theoretical study of degenerate 2PA (D-2PA) in quantum wells, QWs, is presented, along with a new theory of ND 2PA in QWs is developed. Pulsed mid-IR detection of femtosecond pulses is investigated in two different semiconductor p-i-n photodiodes (GaAs and GaN). With the smaller gap materials having larger ND-2PA, it is observed that they have better sensitivity to mid-IR detection, but unwanted background from D-2PA outweighs this advantage. A comparison of responsivity and signal-to-background ratio for GaAs and GaN in END-2PA based detection is presented. END-2PA enhancement is utilized for CW IR detection in uncooled GaAs and GaN p-i-n photodiodes. The pulsed mid-IR detection experiments are further extended to perform mid-IR imaging in uncooled GaN p-i-n photodetectors. A 3-D automated scanning gated imaging system is developed to obtain 3-D mid-IR images of various objects. The gated imaging system allows simultaneous 3-D and 2-D imaging of objects. The 3-D gated imaging system described in the dissertation could be used for examination of buried structures (microchannels, defects etc.) or laser written volumetric structures and could also be suitable for in-vivo imaging applications in biology in the mid-IR spectral region. As an example, 3-D imaging of buried semiconductor structures is presented.A theoretical study of D-2PA of QWs for transverse electric (TE) and transverse magnetic (TM) fields is carried out and an analytical expression for the D-2PA coefficient in QWs using second-order perturbation theory is derived. A theory for ND-2PA in QW semiconductor using second-order perturbation theory is developed for the first time and an analytical expression for the ND-2PA coefficient for TE, TM, and the mixed case of TE and TM is derived. The shape of the 2PA curve for the D-2PA and ND-2PA for QWs in the TE case is similar to that of bulk semiconductors. As governed by the selection rules both the D-2PA and ND-2PA curves for the TE case does not show a step-like signature for the density of states of the QWs whereas 2PA curve for the TM case shows such step like sharp features. The ND-2PA coefficient for TE, TM, and the mixed case is compared with that obtained for bulk semiconductors. Large enhancement in ND-2PA of QW semiconductors for the TM case over bulk semiconductors is predicted.
Show less - Date Issued
- 2015
- Identifier
- CFE0005684, ucf:50164
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005684
- Title
- THREE-PHOTON ABSORPTION PROCESS IN ORGANIC DYES ENHANCED BY SURFACE PLASMON RESONANCE.
- Creator
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Cohanoschi, Ion, Hernandez, Florencio, University of Central Florida
- Abstract / Description
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Multi-photon absorption processes have received significant attention from the scientific community during the last decade, mainly because of their potential applications in optical limiting, data storage and biomedical fields. Perhaps, one of the most investigated processes studied so far has been two-photon absorption (2PA). These investigations have resulted in successful applications in all the fields mentioned above. However, 2PA present some limitations in the biomedical field when...
Show moreMulti-photon absorption processes have received significant attention from the scientific community during the last decade, mainly because of their potential applications in optical limiting, data storage and biomedical fields. Perhaps, one of the most investigated processes studied so far has been two-photon absorption (2PA). These investigations have resulted in successful applications in all the fields mentioned above. However, 2PA present some limitations in the biomedical field when pumping at typical 2PA wavelengths. In order to overcome these limitations, three-photon absorption (3PA) process has been proposed. However, 3PA in organic molecules has a disadvantage, typical values of σ3' are small (10-81 cm6s2/photon2), therefore, 3PA excitation requires high irradiances to induce the promotion of electrons from the ground state to the final excited state. To overcome this obstacle, specific molecules that exhibit large 3PA cross-section must be designed. Thus far, there is a lack of systematic studies that correlate 3PA processes with the molecular structure of organic compounds. In order to fill the existent gap in 3PA molecular engineering, in this dissertation we have investigated the structure/property relationship for a new family of fluorene derivatives with very high three-photon absorption cross-sections. We demonstrated that the symmetric intramolecular charge transfer as well as the -electron conjugation length enhances the 3PA cross-section of fluorene derivatives. In addition, we showed that the withdrawing electron character of the attractor groups in a pull-pull geometry proved greater 3PA cross-section. After looking for alternative ways to enhance the effective σ3' of organic molecules, we investigated the enhancement of two- and three-photon absorption processes by means of Surface Plasmon. We demonstrated an enhancement of the effective two- and three-photon absorption cross-section of an organic compound of 480 and 30 folds, respectively. We proved that the enhancement is a direct consequence of the electric field enhancement at a metal/buffer interface. Next, motivated by the demands for new materials with enhanced nonlinear optical properties, we studied the 3PA of Hematoporphyrin IX and J-aggregate supramolecular systems. As a result, we were able to propose the use of 3PA in photodynamic therapy using Photofrin, the only drug approved by the FDA for PDT.
Show less - Date Issued
- 2006
- Identifier
- CFE0001362, ucf:46981
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001362
- Title
- CHEMICAL STRUCTURE - NONLINEAR OPTICAL PROPERTY RELATIONSHIPS FOR A SERIES OF TWO-PHOTON ABSORBING FLUORENE MOLECULES.
- Creator
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Hales, Joel McCajah, Van Stryland, Eric W., University of Central Florida
- Abstract / Description
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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.
Show less - Date Issued
- 2004
- Identifier
- CFE0000005, ucf:46103
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000005
- Title
- In Actu Et In Silicio: Linear and Nonlinear Photophysical Characterization of a Novel Europium Complex, and Incorporating Computational Calculations in the Analysis of Novel Organic Compounds.
- Creator
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Woodward, Adam, Belfield, Kevin, Campiglia, Andres, Harper, James, Frazer, Andrew, Cheng, Zixi, University of Central Florida
- Abstract / Description
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Despite not being a tangible substance, light is becoming an increasingly valuable tool in numerous areas of science and technology: the use of laser excitation of a fluorescent probe can generate incredibly detailed images of cellular structures without the need for large amounts of dissection; new types of solar cells are being produced using organic dyes to harvest light; computer data can be stored by inducing a chemical change in a compound through irradiation with light. However, before...
Show moreDespite not being a tangible substance, light is becoming an increasingly valuable tool in numerous areas of science and technology: the use of laser excitation of a fluorescent probe can generate incredibly detailed images of cellular structures without the need for large amounts of dissection; new types of solar cells are being produced using organic dyes to harvest light; computer data can be stored by inducing a chemical change in a compound through irradiation with light. However, before any of these materials can be applied in such a way, their properties must first be analyzed for them to be deemed viable.The focus of this dissertation is the photophysical characterization, linear and nonlinear, of a several novel organic compounds, and a europium complex, as well as using quantum chemical calculation techniques to understand some of the phenomena that are witnessed and begin to develop predictive capability. The nonlinear characterization of compounds utilizes wavelengths outside of their linear absorption range, where a focused beam can achieve the same excitation as one at half the wavelength, though this effect has a quadratic dependence on power.The potential for nonlinear excitation, or two-photon absorption (2PA), is becoming of increasing interest and importance for organic chromophores. Exciting only a small volume of material at a focal point makes it possible to nondestructively image samples in 3-dimensions, record data in multiple layers, and fabricate intricate structures through photopolymerization reactions.Lanthanides such as europium are known to exhibit sharp emission bands when excited, typically through an antenna effect due to the low probability of achieving direct excitation. This emission is long-lived, and through gating systems can readily be separated from background noise and autofluorescence (often observed in biological samples) that have much shorter lifetimes. Thus, one of the foci of this dissertation is the photophysical investigation of a series of novel lanthanide complexes, with particular attention to a europium complex.
Show less - Date Issued
- 2014
- Identifier
- CFE0005908, ucf:50891
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005908
- Title
- Structure-Property Relationship of the Two-Photon Circular Dichroism of Compounds with Axial and Helical Chirality.
- Creator
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Diaz, Carlos, Hernandez, Florencio, Uribe Romo, Fernando, Kuebler, Stephen, Masunov, Artem, Del Barco, Enrique, University of Central Florida
- Abstract / Description
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Back in 1894 Lord Kelvin coined the term (")chiral(") in order to refer to molecules whose mirror images were not superimposable with themselves. Over the years, research has demonstrated the important role that chiral molecules play in life, chemistry, and biology as well as their importance in the development of new drugs and technologies.The efforts to understand chiral systems have been mainly driven by spectroscopic methods that leverage on the opposite responses that enantiomers have to...
Show moreBack in 1894 Lord Kelvin coined the term (")chiral(") in order to refer to molecules whose mirror images were not superimposable with themselves. Over the years, research has demonstrated the important role that chiral molecules play in life, chemistry, and biology as well as their importance in the development of new drugs and technologies.The efforts to understand chiral systems have been mainly driven by spectroscopic methods that leverage on the opposite responses that enantiomers have to linear or circularly polarized light of both handedness. More specifically, Electronic Circular Dichroism (ECD) which measures the differences in linear absorption of left and right circularly polarized light has been the method par excellence for the spectroscopic characterization of chiral compounds. Unfortunately, the fact that ECD is based on linear absorption severely limits the use of this method in the near to far UV region. This is mainly due to the interferences generated by the strong linear absorption of common organic solvents and buffers in this portion of the light spectrum. Nevertheless, the fact remains that many chiral biomolecules of interest related to deceases like Alzheimer and Parkinson, exhibit most of their linear absorption in the near to far UV region where ECD cannot be employed for their study. Therefore, it has become an urgent necessity to develop spectroscopic methods to study chiral molecules that can circumvent the limitations of ECD at shorter wavelengths. In order to overcome the existent limitations in linear chiral spectroscopy, the nonlinear equivalent of ECD arises as a promising alternative, i.e. Two-Photon Circular Dichroism (TPCD). Although, this phenomenon was theoretically predicted in 1975, it was not until 2008, with the introduction of the double-L scan, that a reliable and versatile method for the measurement of TPCD was introduced. The high sensitivity of this method is based on the use of (")twin(") pulses that allow accounting for fluctuations in the excitation source that prevented the experimental realization of the measurement. The first measurement of a full TPCD spectrum was performed on BINOL enantiomers and the results were supported and discussed with the help of theoretical calculations. After that seminal work, we embarked in expanding the understanding of the structure-property relationship of TPCD by performing, systematically, a series of theoretical-experimental studies in chiral biaryl derivatives and compounds with helical chirality.In Chapter 2 we present the theoretical-experimental study of the effect of the ?-electron delocalization curvature on the TPCD of molecules with axial chirality. The targeted molecules for this part of our investigation were S-BINOL, S-VANOL, and S-VAPOL. Our findings revealed that an increase in the TPCD signal, within this series of compounds, was related to the curvature of the ?(-)electron delocalization. The contributions of the different transition moments to the two-photon rotatory strength support our outcomes. Then, in Chapter 3 we introduce the development of the Fragment-Recombination Approach (FRA) for the calculation of the TPCD spectra of large molecules. This simple but powerful method is based on the additivity of the TPCD signal, and is subject to a strict conditional fragmentation approach. FRA-TPCD is demonstrated, theoretically, in two hypothetical molecular systems from the biaryl derivatives family. Afterward, in Chapter 4 we show the first experimental demonstration of FRA-TPCD through the conformational analysis of an axially-chiral Salen ligand in solution (AXF-155). The FRA-TPCD spectra calculated for the different isomers of AXF-155 allowed narrowing the number of possible isomers of this complex molecule in THF solution to only two. This represents a significant improvement from previously reported results using ECD. Subsequently, in Chapter 5 we present the study of the effect of intramolecular charge transfer (ICT) in S-BINAP, an axially dissymmetric diphosphine ligand with strong ICT. The evaluation of the performance of two different exchange-correlation functional (XCF) confirmed that in order to properly predict the theoretical TPCD spectrum of a molecule exhibiting strong ICT, it is required to use an XCF such as CAM-B3LYP. In addition, our findings revealed the importance of considering an adequate number of excited states in order to be able to fully reproduce the experimental TPCD spectrum, thus avoiding wrong assignments of theoretical transitions to experimental spectral features. Finally, and expanding on our previous study, in Chapter 6 we investigated the effect of the nature of ICT on two hexahelicene derivatives. Our investigation demonstrated that the TPCD signal of chiral molecules with strong ICT does not only depend on the strength of this effect but on its nature, i.e. extension of the ?(-)electronic delocalization increasing beyond (EXO-ICT) or within (ENDO-ICT) the helicene core. In summary, with the results presented in this thesis we closed a first loop in the understanding of the structure-property relationship of TPCD. In the future, we expect to deepen in our knowledge of the structure-property relationship of this phenomenon by studying further helicene derivatives with donor-acceptor motif, and through the application of FRA-TPCD to the conformational analysis of amino acids in peptides. We foresee numerous applications of TPCD for the study of optically active molecules with implications in biology, medicine, and the drug and food industry, and applications in nanotechnology, asymmetric catalysis and photonics.
Show less - Date Issued
- 2015
- Identifier
- CFE0005787, ucf:50067
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005787
- Title
- NONLINEAR OPTICAL PROPERTIES OF ORGANIC CHROMOPHORES CALCULATED WITHIN TIME DEPENDENT DENSITY FUNCTIONAL THEORY.
- Creator
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Tafur, Sergio, Kokoouline, Viatcheslav, University of Central Florida
- Abstract / Description
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Time Dependent Density Functional Theory offers a good accuracy/computational cost ratio among different methods used to predict the electronic structure for molecules of practical interest. The Coupled Electronic Oscillator (CEO) formalism was recently shown to accurately predict Nonlinear Optical (NLO) properties of organic chromophores when combined with Time Dependent Density Functional Theory. Unfortunately, CEO does not lend itself easily to interpretation of the structure activity...
Show moreTime Dependent Density Functional Theory offers a good accuracy/computational cost ratio among different methods used to predict the electronic structure for molecules of practical interest. The Coupled Electronic Oscillator (CEO) formalism was recently shown to accurately predict Nonlinear Optical (NLO) properties of organic chromophores when combined with Time Dependent Density Functional Theory. Unfortunately, CEO does not lend itself easily to interpretation of the structure activity relationships of chromophores. On the other hand, the Sum Over States formalism in combination with semiempirical wavefunction methods has been used in the past for the design of simplified essential states models. These models can be applied to optimization of NLO properties of interest for applications. Unfortunately, TD-DFT can not be combined directly with SOS because state-to-state transition dipoles are not defined in the linear response TD approach. In this work, a second order CEO approach to TD-DFT is simplified so that properties of double excited states and state-to-state transition dipoles may be expressed through the combination of linear response properties. This approach is termed the a posteriori Tamm-Dancoff approximation (ATDA), and validated against high-level wavefunction theory methods. Sum over States (SOS) and related Two-Photon Transition Matrix formalism are then used to predict Two-Photon Absorption (2PA) profiles and anisotropy, as well as Second Harmonic Generation (SHG) properties. Numerical results for several conjugated molecules are in excellent agreement with CEO and finite field calculations, and reproduce experimental measurements well.
Show less - Date Issued
- 2007
- Identifier
- CFE0001853, ucf:47372
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001853
- Title
- EXPERIMENTAL AND THEORETICAL STUDY OF THE OPTICAL PROPERTIES OF SEMICONDUCTOR QUANTUM DOTS.
- Creator
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Nootz, Gero, Cuenya , Beatriz, University of Central Florida
- Abstract / Description
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The aim of this dissertation is to gain a better understanding of the unique electronic structure of lead salt quantum dots (QDs) and its influences on the nonlinear optical (NLO) properties as well as the time dynamics of the photogenerated charge carriers. A variety of optical techniques such as Z-scan, two-photon excited fluorescence and time-resolved pump probe spectroscopy are used to measure these properties. The one-photon as well as the degenerate and nondegenerate two-photon...
Show moreThe aim of this dissertation is to gain a better understanding of the unique electronic structure of lead salt quantum dots (QDs) and its influences on the nonlinear optical (NLO) properties as well as the time dynamics of the photogenerated charge carriers. A variety of optical techniques such as Z-scan, two-photon excited fluorescence and time-resolved pump probe spectroscopy are used to measure these properties. The one-photon as well as the degenerate and nondegenerate two-photon absorption (2PA) spectra are measured and the electronic wave functions from a four-band envelope function formalism are used to model the results. We observe local maxima in the 2PA spectra for QD samples of many different sizes at energies where only 1PA is predicted by the model. This is similar to the previously measured transitions in the 1PA spectra which are not predicted by the model but accrue at the energies of the two-photon allowed transitions. Most importantly we observe 2PA peaks for all samples at the energy of the first one-photon allowed transition. This result can only be understood in terms of symmetry breaking and therefore is strong evidence that other transitions, not predicted by the model if the selection rules are left intact, also have the origin in the lifted spatial symmetry of the wave functions. On the other hand, the uniquely symmetric eigenenergies of these quantum-confined energy states in the conduction and valance bands explain the observed trend toward larger two-photon cross-sections as the quantum confinement is increased in smaller QDs. Moreover, this unique feature is shown to reduce the possible relaxation channels for photoexcited carriers, which is confirmed experimentally by the reduced carrier relaxation rate as compared to CdSe QDs which lack this symmetry. Carrier multiplication (CM), a process in which several electrons are excited by the absorption of a single photon is studied in PbS QDs. We show that for PbS QDs with radius smaller than 2.5 nm the parameters of CM get very close to the theoretical optimum. Next-generation solar cells operating under these ideal conditions could potentially have conversion efficiency of up to 42%. This compares favorably to the 30% efficiency limit of a single junction silicon solar cell.
Show less - Date Issued
- 2010
- Identifier
- CFE0003396, ucf:48413
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003396
- Title
- Quantum Chemical Studies for the Engineering of Metal Organic Materials.
- Creator
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Rivera Jacquez, Hector, Masunov, Artem, Balaeff, Alexander, Harper, James, Heider, Emily, Zou, Shengli, Kaden, William, University of Central Florida
- Abstract / Description
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Metal Organic Materials (MOM) are composed of transition metal ions as connectors and organic ligands as linkers. MOMs have been found to have high porosity, catalytic, and optical properties. Here we study the gas adsorption, color change, and non-linear optical properties of MOMs. These properties can be predicted using theoretical methods, and the results may provide experimentalists with guidance for rational design and engineering of novel MOMs. The theory levels used include semi...
Show moreMetal Organic Materials (MOM) are composed of transition metal ions as connectors and organic ligands as linkers. MOMs have been found to have high porosity, catalytic, and optical properties. Here we study the gas adsorption, color change, and non-linear optical properties of MOMs. These properties can be predicted using theoretical methods, and the results may provide experimentalists with guidance for rational design and engineering of novel MOMs. The theory levels used include semi-empirical quantum mechanical calculations with the PM7 Hamiltonian and, Density Functional Theory (DFT) to predict the geometry and electronic structure of the ground state, and Time Dependent DFT (TD-DFT) to predict the excited states and the optical properties.The molecular absorption capacity of aldoxime coordinated Zn(II) based MOMs (previously measured experimentally) is predicted by using PM7 Theory level. The 3D structures were optimized with and without host molecules inside the pores. The absorption capacity of these crystals was predicted to be 8H2 or 3N2 per unit cell. When going beyond this limit, the structural integrity of the bulk material becomes fractured and microcrystals are observed both experimentally and theoretically.The linear absorption properties of Co(II) based complexes are known to change color when the coordination number is altered. In order to understand the mechanism of this color change TD-DFT methods are employed. The chromic behavior of the Co(II) based complexes studied was confirmed to be due to a chain in coordination number that resulted in lower metal to ligand distances. These distances destabilize the occupied metal d orbitals, and as a consequence of this, the metal to ligand transition energy is lowered enough to allow the crystals to absorb light at longer wavelengths.Covalent organic frameworks (COFs) present an extension of MOM principles to the main group elements. The synthesis of ordered COFs is possible by using predesigned structures andcarefully selecting the building blocks and their conditions for assembly. The crystals formed by these systems often possess non-linear optical (NLO) properties. Second Harmonic Generation (SHG) is one of the most used optical processes. Currently, there is a great demand for materials with NLO optical properties to be used for optoelectronic, imaging, sensing, among other applications. DFT calculations can predict the second order hyperpolarizability ?2 and tensor components necessary to estimate NLO. These calculations for the ?2 were done with the use of the Berry's finite field approach. An efficient material with high ?2 was designed and the resulting material was predicted to be nearly fivefold higher than the urea standard.Two-photon absorption (2PA) is another NLO effect. Unlike SHG, it is not limited to acentric material and can be used development of in vivo bio-imaging agents for the brain. Pt(II) complexes with porphyrin derivatives are theoretically studied for that purpose. The mechanism of 2PA enhancement was identified. For the most efficient porphyrin, the large 2PA cross-section was found to be caused by a HOMO-LUMO+2 transition. This transition is strongly coupled to 1PA allowed Q-band HOMO-LUMO states by large transition dipoles. Alkyl carboxyl substituents delocalize the LUMO+2 orbital due to their strong ?-acceptor effect, enhancing transition dipoles and lowering the 2PA transition to the desirable wavelengths range.The mechanism 2PA cross-section enhancement of aminoxime and aldoxime ligands upon metal addition of is studied with TD-DFT methods. This mechanism of enhancement is found to be caused by the polarization of the ligand orbitals by the metal cation. After polarization an increase in ligand to ligand transition dipole moment. This enhancement of dipole moment is related to the increase in 2PA cross-sections.
Show less - Date Issued
- 2015
- Identifier
- CFE0005990, ucf:50777
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005990
- Title
- Prediction of Optical Properties of Pi-Conjugated Organic Materials for Technological Innovations.
- Creator
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Nayyar, Iffat, Masunov, Artem, Saha, Haripada, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
- Abstract / Description
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Organic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged ...
Show moreOrganic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged (polaronic) excitations. In this work, we investigate the appropriate theoretical methods used for the (a) prediction of 2PA properties for rational design of organic materials with improved NLO properties, and (b) understanding of the essential electronic excitations controlling the energy-transfer and charge-transport properties in organic optoelectronics. Accurate prediction of these electro-optical properties is helpful for structure-activity relationships useful for technological innovations.In Chapter 1 we emphasize on the potential use of the organic materials for these two applications. The 2PA process is advantageous over one-photon absorption for deep-tissue fluorescence microscopy, photodynamic therapy, microfabrication and optical data storage owing to the three-dimensional spatial selectivity and improved penetration depth in the absorbing or scattering media. The design of the NLO materials with large 2PA cross-sections may reduce the optical damage due to the use of the high intensity laser beams for excitation. The organic molecules also possess self-localized excited states which can decay radiatively or nonradiatively to form excitonic states. This suggests the use of these materials in the electroluminescent devices such as light-emitting diodes and photovoltaic cells through the processes of exciton formation or dissociation, respectively. It is therefore necessary to understand ultrafast relaxation processes required in understanding the interplay between the efficient radiative transfer between the excited states and exciton dissociation into polarons for improving the efficiency of these devices. In Chapter 2, we provide the detailed description of the various theoretical methods applied for the prediction as well as the interpretation of the optical properties of a special class of substituted PPV [poly (p-phenylene vinylene)] oligomers. In Chapter 3, we report the accuracy of different second and third order time dependent density functional theory (TD-DFT) formalisms in prediction of the 2PA spectra compared to the experimental measurements for donor-acceptor PPV derivatives. We recommend a posteriori Tamm-Dancoff approximation method for both qualitative and quantitative analysis of 2PA properties. Whereas, Agren's quadratic response methods lack the double excitations and are not suitable for the qualitative analysis of the state-specific contributions distorting the overall quality of the 2PA predictions. We trace the reasons to the artifactual excited states above the ionization threshold. We also study the effect of the basis set, geometrical constraints and the orbital exchange fraction on the 2PA excitation energies and cross-sections. Higher exchange (BMK and M05-2X) and range-separated (CAM-B3LYP) hybrid functionals are found to yield inaccurate predictions both quantitatively and qualitatively. The failure of the exchange-correlation (XC) functionals with correct asymptotic is traced to the inaccurate transition dipoles between the valence states, where functionals with low HF exchange succeed. In Chapter 4, we test the performance of different semiempirical wavefunction theory methods for the prediction of 2PA properties compared to the DFT results for the same set of molecules. The spectroscopic parameterized (ZINDO/S) method is relatively better than the general purpose parameterized (PM6) method but the accuracy is trailing behind the DFT methods. The poor performances of PM6 and ZINDO/S methods are attributed to the incorrect description of excited-to-excited state transition and 2PA energies, respectively. The different semiempirical parameterizations can at best be used for quantitative analysis of the 2PA properties. The ZINDO/S method combined with different orders of multi-reference configuration interactions provide an improved description of 2PA properties. However, the results are observed to be highly dependent on the specific choice for the active space, order of excitation and reference configurations.In Chapter 5, we present a linear response TD-DFT study to benchmark the ability of existing functional models to describe the extent of self-trapped neutral and charged excitations in PPV and its derivative MEH-PPV considered in their trans-isomeric forms. The electronic excitations in question include the lowest singlet (S1) and triplet (T1†) excitons, positive (P+) and negative (P-) polarons and the lowest triplet (T1) states. Use of the long-range-corrected DFT functional, such as LC-wPBE, is found to be crucial in order to predict the physically correct spatial localization of all the electronic excitations in agreement with experiment. The inclusion of polarizable dielectric environment play an important role for the charged states. The particle-hole symmetry is preserved for both the polymers in trans geometries. These studies indicate two distinct origins leading to self-localization of electronic excitations. Firstly, distortion of molecular geometry may create a spatially localized potential energy well where the state wavefunction self-traps. Secondly, even in the absence of geometric and vibrational dynamics, the excitation may become spatially confined due to energy stabilization caused by polarization effects from surrounding dielectric medium.In Chapter 6, we aim to separate these two fundamental sources of spatial localization. We observe the electronic localization of P+ and P- is determined by the polarization effects of the surrounding media and the character of the DFT functional. In contrast, the self-trapping of the electronic wavefunctions of S1 and T1(T1†) mostly follows their lattice distortions. Geometry relaxation plays an important role in the localization of the S1 and T1† excitons owing to the non-variational construction of the excited state wavefunction. While, mean-field calculated P+, P- and T1 states are always spatially localized even in ground state S0 geometry. Polaron P+ and P- formation is signified by the presence of the localized states for the hole or the electron deep inside the HOMO-LUMO gap of the oligomer as a result of the orbital stabilization at the LC-wPBE level. The broadening of the HOMO-LUMO band gap for the T1 exciton compared to the charged states is associated with the inverted bond length alternation observed at this level. The molecular orbital energetics are investigated to identify the relationships between state localization and the corresponding orbital structure.In Chapter 7, we investigate the effect of various conformational defects of trans and cis nature on the energetics and localization of the charged P+ and P- excitations in PPV and MEH-PPV. We observe that the extent of self-trapping for P+ and P- polarons is highly sensitive on molecular and structural conformations, and distribution of atomic charges within the polymers. The particle-hole symmetry is broken with the introduction of trans defects and inclusion of the polarizable environment in consistent with experiment. The differences in the behavior of PPV and MEH-PPV is rationalized based on their orbital energetics and atomic charge distributions. We show these isomeric defects influence the behavior and drift mobilities of the charge carriers in substituted PPVs.
Show less - Date Issued
- 2013
- Identifier
- CFE0005110, ucf:50722
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005110