This thesis describes the computational tools that allow the simulation of polymers made up of an arbitrary number of three-level systems, the study of such systems and comparisons to experimental nonlinear optical spectra. The three-level system generator (3LSG), is designed to automatically generate the operators that describe the system, whether it is a closed system or an open quantum system (OQS) in contact with a bath, with just a few input parameters. A user is free to specify each 3LS's energy levels and transition dipoles between said levels, site couplings between the different units of the polymer and in the case of open systems, the rates and couplings describing the different relaxation processes taking place in an OQS, using the Redfield formalism. In either cases, the 3LSG is then capable of generating the Hamiltonian 𝐻₀ describing the closed system or the Liouvillian 𝓛₀ describing the open system from the various inputs. The Ultrafast Spectroscopy Suite (UFSS) is an open-source software suite used to perform the nonlinear optical spectroscopies simulations. It contains 4 main modules, one of which is the Hamiltonian/Liouvillian Generator (HLG), a module previously designed to model simpler two-level systems. The 3LSG is a sub-module of the HLG. The three-level system generator is used to replicate a theoretical model describing a copolymer model made of many identical pairs of squaraine monomers, where each monomer is a three-level system interacting with its neighbouring sites and a surrounding bath. The system automatically generated by the 3LSG is used, along with other spectroscopic calculation tools, to simulate high-order transient absorption (TA) spectroscopies and study the long-time behaviour of the 3rd-order to 13th-order excited state absorption (ESA) peaks in the TA signals. The 3LSG is used in conjunction with spectroscopic calculations tools as it was originally intented, though it may also be used by itself to study Hamiltonians and Liouvillians of electronic three-level systems.

Thesis (Ph. D.)--Michigan State University. Dept. of Chemistry, 2008. / Title from PDF t.p. (viewed Sept. 10, 2009). Includes bibliographical references. Also issued in print.

Thesis (PhD)--Montana State University--Bozeman, 2010. / Typescript. Chairperson, Graduate Committee: Aleksander Rebane. Includes bibliographical references (leaves 126-144).

This thesis presents analytic and computational advances in the prediction of perturbative nonlinear optical spectroscopies. The contributions of this thesis are packaged together in an open source, freely available piece of software called ultrafast spectroscopy suite (UFSS). It is designed to automatically simulate nonlinear optical spectroscopies for any phase-matching or phase-cycling condition, including finite pulse effects. UFSS includes an algorithm called the diagram generator (DG) that automates the process of writing out all of the Feynman diagrams that contribute to a desired phase-matching or phase-cycling condition, and includes all pulse overlap diagrams when relevant, paving the way toward automation of perturbative calculations. Further, many diagrams can be automatically combined into composite diagrams, giving an exponential decrease in computation time of high-order calculations. Composite diagrams even allow for the efficient study of Rabi oscillations as a function of pulse amplitude, by summing many orders of perturbation theory. The perturbative calculations are done using a novel algorithm presented in this thesis called Ultrafast Ultrafast spectroscopy (UF2). UF2 is an efficient method for determining diagrammatic contributions to spectra including arbitrary (whether analytical or experimentally measured) pulse shapes. It uses the speed of the fast Fourier transform to be as much as 500 times faster than direct propagation techniques for small model Hamiltonians (for Hamiltonian dimension of 100 or less). UF2 outperforms direct propagation techniques for a wide range of model systems, with the speed boost diminishing as the dimension of the model Hamiltonian increases. UF2 can predict spectra for any model system whose relevant Hilbert space that can be described using a finite basis and that can be diagonalized numerically, and users are free to specify their own model. UFSS includes a model generator that generates Hamiltonians and Liouvillians of vibronic systems, allowing users to easily simulate NLOSs for a wide range of model system parameters. UFSS is a fully functional piece of software for simulating any NLOS, to any desired order in perturbation theory.

Thesis (Ph. D.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

The development of efficient solar energy conversion devices has attracted much attention. Despite the fact that progress have been achieved, a fundamental understanding examining why efficiency can be improved remains elusive. For example, dye-sensitized solar cells (DSSC) exhibit high conversion efficiency when acetonitrile is used to prepare both the working electrode and the electrolyte. However, the mechanism explaining exactly how solvent influences device performance has not yet been systematically investigated. Another prominent example is the metal/semiconductor heterojunction systems. While it has been demonstrated that such mixed systems can significantly improve solar conversion efficiency, the mechanism of the electron dynamics driving these systems remains controversial. This stems in part from the fact that the experimentally deduced time constants, which are characteristic of such systems, are only ever extracted from phenomenological models and therefore cannot be assigned to specific physical processes. Ultimately, the development of a physical model is necessary to obtain an unambiguous physical picture of the solar conversion process. In this dissertation, the ultrafast nonlinear spectroscopic methods, second harmonic light scattering (SHS) and transient absorption (TA) spectroscopy, have been employed to study dye molecular adsorption and charge transfer dynamics in several solar energy conversion systems, including 1) DSSC, where solvent effects are investigated to understand why acetonitrile is the most effective solvent; 2) Ag/TiO2 heterostructure system, where a physical model is proposed to quantitively analyze the electron dynamics; 3) porphyrin/Ag/TiO2 nanocomposite, where we found there is no electron injection from porphyrin to TiO2 and plasmonic metal can enhance the porphyrin dye adsorption to improve the device efficiency. The propensity for surface adsorption of two related dyes, ortho-ethyl red (o-ER) and para-ethyl red (p-ER), onto TiO2 particles is studied with SHS. While p-ER readily adsorbs onto TiO2, o-ER does not. It is suggested that this difference is linked to the effects of the steric hindrance of the adsorbate. The influence of the solvent on the adsorption of p-ER onto TiO2 is also investigated. Of significance, p-ER can only chemically bond to the TiO2 surface in aprotic solvents, where adsorption free energy scales with solvent polarity. For protic solvents, preferential adsorption of the solvent shell ultimately prevents direct adsorption of p-ER onto the surface of TiO2. Likewise, solvent effects on charge transfer from p-ER to TiO2 are studied by TA. The electron injection rate is shown to be positively related to solvent polarity. Overall, highly polar aprotic solvents are shown to facilitate dye adsorption and electron injection, which helps improve the efficiency of DSSC devices. Ultrafast dynamics of plasmon-induced hot electrons from Ag to TiO2 nanorods are probed by TA. The observed transient signal, which corresponds to the lifetime of the optically generated electrons, is analyzed using a physical model including electron injection, relaxation, band edge annihilation, the surface to bulk diffusion, and back diffusion from the bulk to the surface. A ca. 13 fs electron injection time is deduced for Ag to TiO2, which is faster than that generated in Au and dyes. Additionally, the excited state exciton dynamics of a porphyrin J-aggregate are investigated and subsequently modeled. More rapid dynamics are found following aggregation of the porphyrin, which can be attributed to the inclusion of more efficient relaxation channels. However, no electron injection from the J-aggregate to TiO2 is observed. This likely stems from the negatively charged repulsion between the two components. Further, when the J-aggregate is introduced into an Ag/TiO2 system, optical excitation occurs predominantly in the J-aggregate. This stems either from direct excitation of the J-aggregate or indirect excitation through plasmon-induced resonant energy transfer from Ag. Our results indicate that plasmon can enhance the dye adsorption, which has great potential for designing more efficient plasmonic DSSC devices. / Chemistry

Nos últimos anos, materiais orgânicos tem ganhado grande interesse em áreas que envolvem espectroscopia óptica não linear. Isso se dá devido aos materiais possuirem consideráveis efeitos ópticos não lineares, apresentarem facilidade de síntese e possuirem propriedades fotofísicas e fotoquímicas que os tornam capazes de serem empregados em um vasto número de possíveis aplicações. Entre os materiais orgânicos, é possível destacar as Porfirinas e Ftalocianinas. A síntese desses materiais possibilita um grande número de classes ou grupos distintos, os quais podem ser distinguidos por suas estruturas periféricas e/ou íons metálicos que podem ser inseridos no interior dos macrociclos. Isso resulta em alterações das suas propriedades ópticas, ou seja, através de alterações das estruturas químicas das Porfirinas e Ftalocianinas é possível modelar suas propriedades ópticas, e assim, de acordo com essas propriedades, discriminar em quais aplicações podem ser empregados. Tais materiais, tendo em vista suas propriedades fotofísicas, podem ser empregados como fotossensitizadores na terapia fotodinâmica, células solares, limitadores ópticos ou fotobactericidas entre outras mais. Sendo assim, nesta Dissertação de Mestrado é realizado uma caracterização espectroscópica linear e não linear desses materiais, para assim deterinar propriedades ópticas específicas que podem ser empregadas nas aplicações citadas. Para tal caracterização espectroscópica, foram empregadas técnicas de espectroscopia linear e não linear, dentre elas a técnica de Varredura-Z foi empregada em três configurações distintas (Varredura-Z por Pulso Único, por Trem de Pulsos e por Luz Branca Supercontínua) para determinação de absorções de estados excitados. Tempos de vida de fluorescência, tempos de decaimento radiativo e de conversão interna, seções de choque de absorção de estado singleto e tripleto (fundamental e excitado) e eficiências quânticas (fluorescência, conversão interna e converção para tripleto) foram os parâmetros determinados e, assim, através desses parâmetros, foi possível entender como alterações nas estruturas químicas (periféricas e íons metálicos) influenciam consideravelmente as propriedades de Porfirinas e Ftalocianinas. / In last years, organic materials have won great interest in areas involving non-linear optical spectroscopy. This is due to the fact that the materials have considerable non-linear optical effects, are easy to synthesize, and have photophysical and photochemical properties that make them capable of being used in a wide range of possible applications. Among the organic materials, it is possible to highlight Porphyrins and Phthalocyanines. The synthesis of these materials enables a large number of distinct classes or groups, which can be distinguished by their peripheral structures and / or metal ions that can be inserted into the macrocycles. It results in changes of its optical properties, that is, replacing the chemical structures of such Porphyrins and Phthalocyanines, it is possible to tune its optical properties, and thus, according to these properties, to discriminate in which applications they can be used. Such materials, in view of their photophysical properties, can be used as photosensitizers in photodynamic therapy, solar cells, optical limiters or photobactericides among others. Thus, in this Master\'s Dissertation, a linear and nonlinear spectroscopic characterization of these materials is carried out in order to determine specific optical properties that can be employed in the cited applications. For this spectroscopic characterization, linear and nonlinear spectroscopy techniques were employed, among them the Z-Scan technique was employed in three distinct configurations (Z-Scan by Single Pulse, by Pulse Train and by Supercontinuum White Light) for determination of absorptions of excited states. Fluorescence lifetimes, radiative decay and internal conversion times, single and triple triplet (fundamental and excited) and quantum efficiencies (fluorescence, internal conversion, and triplet formation) were the parameters determined, and with these parameters, it was possible to understand how changes in the chemical structures (peripheral and metallic ions) modify considerable the optical properties of Porphyrins and Phthalocyanines.

Nos últimos anos, materiais orgânicos tem ganhado grande interesse em áreas que envolvem espectroscopia óptica não linear. Isso se dá devido aos materiais possuirem consideráveis efeitos ópticos não lineares, apresentarem facilidade de síntese e possuirem propriedades fotofísicas e fotoquímicas que os tornam capazes de serem empregados em um vasto número de possíveis aplicações. Entre os materiais orgânicos, é possível destacar as Porfirinas e Ftalocianinas. A síntese desses materiais possibilita um grande número de classes ou grupos distintos, os quais podem ser distinguidos por suas estruturas periféricas e/ou íons metálicos que podem ser inseridos no interior dos macrociclos. Isso resulta em alterações das suas propriedades ópticas, ou seja, através de alterações das estruturas químicas das Porfirinas e Ftalocianinas é possível modelar suas propriedades ópticas, e assim, de acordo com essas propriedades, discriminar em quais aplicações podem ser empregados. Tais materiais, tendo em vista suas propriedades fotofísicas, podem ser empregados como fotossensitizadores na terapia fotodinâmica, células solares, limitadores ópticos ou fotobactericidas entre outras mais. Sendo assim, nesta Dissertação de Mestrado é realizado uma caracterização espectroscópica linear e não linear desses materiais, para assim deterinar propriedades ópticas específicas que podem ser empregadas nas aplicações citadas. Para tal caracterização espectroscópica, foram empregadas técnicas de espectroscopia linear e não linear, dentre elas a técnica de Varredura-Z foi empregada em três configurações distintas (Varredura-Z por Pulso Único, por Trem de Pulsos e por Luz Branca Supercontínua) para determinação de absorções de estados excitados. Tempos de vida de fluorescência, tempos de decaimento radiativo e de conversão interna, seções de choque de absorção de estado singleto e tripleto (fundamental e excitado) e eficiências quânticas (fluorescência, conversão interna e converção para tripleto) foram os parâmetros determinados e, assim, através desses parâmetros, foi possível entender como alterações nas estruturas químicas (periféricas e íons metálicos) influenciam consideravelmente as propriedades de Porfirinas e Ftalocianinas. / In last years, organic materials have won great interest in areas involving non-linear optical spectroscopy. This is due to the fact that the materials have considerable non-linear optical effects, are easy to synthesize, and have photophysical and photochemical properties that make them capable of being used in a wide range of possible applications. Among the organic materials, it is possible to highlight Porphyrins and Phthalocyanines. The synthesis of these materials enables a large number of distinct classes or groups, which can be distinguished by their peripheral structures and / or metal ions that can be inserted into the macrocycles. It results in changes of its optical properties, that is, replacing the chemical structures of such Porphyrins and Phthalocyanines, it is possible to tune its optical properties, and thus, according to these properties, to discriminate in which applications they can be used. Such materials, in view of their photophysical properties, can be used as photosensitizers in photodynamic therapy, solar cells, optical limiters or photobactericides among others. Thus, in this Master\'s Dissertation, a linear and nonlinear spectroscopic characterization of these materials is carried out in order to determine specific optical properties that can be employed in the cited applications. For this spectroscopic characterization, linear and nonlinear spectroscopy techniques were employed, among them the Z-Scan technique was employed in three distinct configurations (Z-Scan by Single Pulse, by Pulse Train and by Supercontinuum White Light) for determination of absorptions of excited states. Fluorescence lifetimes, radiative decay and internal conversion times, single and triple triplet (fundamental and excited) and quantum efficiencies (fluorescence, internal conversion, and triplet formation) were the parameters determined, and with these parameters, it was possible to understand how changes in the chemical structures (peripheral and metallic ions) modify considerable the optical properties of Porphyrins and Phthalocyanines.

This dissertation investigates two long standing issues in nonlinear optics: complete characterization of the ultrafast dynamics of simple molecules, and the potential of a two-photon laser using a bulk semiconductor gain medium. Within the Born-Oppenheimer approximation, nonlinear refraction in molecular liquids and gases can arise from both bound-electronic and nuclear origins. Knowledge of the magnitudes, temporal dynamics, polarization and spectral dependences of each of these mechanisms is important for many applications including filamentation, white-light continuum generation, all-optical switching, and nonlinear spectroscopy. In this work the nonlinear dynamics of molecules are investigated in both liquid and gas phase with the recently developed beam deflection technique which measures nonlinear refraction directly in the time domain. Thanks to the utility of the beam deflection technique we are able to completely determine the third-order response function of one of the most important molecular liquids in nonlinear optics, carbon disulfide. This allows the prediction of essentially any nonlinear refraction or two-photon absorption experiment on CS2. Measurements conducted on air (N2 and O2) and gaseous CS2 reveal coherent rotational revivals in the degree of alignment of the ensemble at a period that depends on its moment of inertia. This allows measurement of the rotational and centrifugal distortion constants of the isolated molecules. Additionally, the rotational contribution to the beam deflection measurement can be eliminated thanks to the particular polarization dependence of the mechanism. At a specific polarization, the dominant remaining contribution is due to the bound-electrons. Thus both the bound-electronic nonlinear refractive index of air, and second hyperpolarizability of isolated CS2 molecules, are measured directly. The later agrees well with liquid CS2 measurements, where local field effects are significant. The second major portion of this dissertation addresses the possibility of using bulk semiconductors as a two-photon gain medium. A two-photon laser has been a goal of nonlinear optics since shortly after the original laser*s development. In this case, two-photons are emitted from a single electronic transition rather than only one. This processes is known as two-photon gain (2PG). Semiconductors have large two-photon absorption coefficients, which are enhanced by ~2 orders of magnitude when using photons of very different energies, e.g., ћωa≈10ћωb. This enhancement should translate into large 2PG coefficients as well, given the inverse relationship between absorption and gain. Here, we experimentally demonstrate both degenerate and nondegenerate 2PG in optically excited bulk GaAs via pump-probe experiments. This constitutes, to my knowledge, the first report of nondegenerate two-photon gain. Competition between 2PG and competing processes, namely intervalence band and nondegenerate three-photon absorption (ND-3PA), in both cases are theoretically analyzed. Experimental measurements of ND-3PA agree with this analysis and show that it is enhanced much more than ND-2PG. It is found for both degenerate and nondegenerate photon pairs that the losses dominate the two-photon gain, preventing the possibility of a two-photon semiconductor laser.

Understanding molecular interactions at the surfaces of cellular membranes, including adsorption and transport, is of fundamental importance in both biological and pharmaceutical studies. At present, particularly with respect to small and medium size (drug-like) molecules, it is desirable to gain an understanding of the mechanisms that govern membrane adsorption and transport. To characterize drug-membrane interactions and mechanisms governing the process of molecular uptake at cellular membranes in living organisms, we need to develop effective experimental techniques to reach quantitative and time-resolved analysis of molecules at the membrane surfaces. Also, we preferably want to develop label-free optical techniques suited for single-cell and live cell analysis. Here, I discuss the nonlinear optical technique, second-harmonic light scattering (SHS), for studying molecule-membrane interactions and transport of molecules at the membrane of living cells with real-time resolution and membrane surface-specificity. Time-resolved SHS can quantify adsorption and transport of molecules, with specific nonlinear optical properties, at living organisms without imposing any mechanical stress onto the membrane. This label-free and surface-sensitive technique can even differentiate molecular transport at individual membranes within a multi-membrane cell (e.g., bacteria). In this dissertation, I present our current research and accomplishments in extending the capabilities of the SHS technique to study molecular uptake kinetics at the membranes of living cells, to monitor bacteria membrane integrity, to characterize the antibacterial mechanism-of-action of antibiotic compounds, to update the molecular mechanism of the Gram-stain protocol, to pixel-wise mapping of the membrane viscosity of the living cells, and to probe drug-induced activation of bacterial mechanosensitive channels in vitro. / Chemistry