This thesis represents a quantum chemical treatise ofvarious types of interactions between radiation and molecularsystems, with special emphasis on the nonlinear opticalprocesses of Multi-Photon Absorption and Excited StateAbsorption. Excitation energies, transition dipole moments,two-photon and three-photon tensor elements have beencalculated from different approaches; density functional theoryandab-initiotheory, employing different orders ofcorrelation treatment with the purpose to provide accuratevalues as well as evaluate the quality of the lower ordermethods. A combined study of the Multi-Photon Absorption andExcited State Absorption processes is motivated partly becausethey both contribute to the total optical response of a systemsubjected to intense radiation, but also because of theirconnection through so-called sum-over-states expressions. Thelatter feature is exploited in a generalized few-states model,which incorporates the polarization of the light and thedirections of the transition dipole moments constructing anexcitation channel, which thereby enables a more comprehensivecomparison of the attained transition dipole moments withexperimental data. Moreover, by decomposing a complex nonlinearresponse process such as Two-Photon Absorption into moreintuitive quantities, generalized few-states models may alsoenable a more elaborate interpretation of computed orexperimental results from which guidelines can be extracted inorder to control or optimize the property of interest. Ageneral conclusion originating from these models is that thetransition dipole moments in an excitation channel should bealigned in order to maximize the Two-Photon Absorptionprobability. The computational framework employed is responsetheory which through the response functions (linear, quadratic,cubic) offers alternative routes for evaluating the propertiesin focus; either directly and untruncated through the singleresidue of the quadratic or cubic response func- tions orthrough various schemes of truncated sum-over-statesexpressions where the key ingredients, transition dipolemoments, can be identified from the single residue of thelinear response function and double residue of the quadraticresponse function. The range of systems treated in the thesisstretches from diatomics, such as carbon monoxide and lithiumhydride, via small to large fundamental organic molecules, suchas formaldehyde, tetrazine and the trans-polyenes, to largechro- mophores, such astrans-stilbene, cumulenes, dithienothiophene,paracyclophane and organo-metallic systems, such as theplatinum(II)ethynyl compounds. / QC 20120320

<p>This thesis represents a quantum chemical treatise ofvarious types of interactions between radiation and molecularsystems, with special emphasis on the nonlinear opticalprocesses of Multi-Photon Absorption and Excited StateAbsorption. Excitation energies, transition dipole moments,two-photon and three-photon tensor elements have beencalculated from different approaches; density functional theoryand<i>ab-initio</i>theory, employing different orders ofcorrelation treatment with the purpose to provide accuratevalues as well as evaluate the quality of the lower ordermethods. A combined study of the Multi-Photon Absorption andExcited State Absorption processes is motivated partly becausethey both contribute to the total optical response of a systemsubjected to intense radiation, but also because of theirconnection through so-called sum-over-states expressions. Thelatter feature is exploited in a generalized few-states model,which incorporates the polarization of the light and thedirections of the transition dipole moments constructing anexcitation channel, which thereby enables a more comprehensivecomparison of the attained transition dipole moments withexperimental data. Moreover, by decomposing a complex nonlinearresponse process such as Two-Photon Absorption into moreintuitive quantities, generalized few-states models may alsoenable a more elaborate interpretation of computed orexperimental results from which guidelines can be extracted inorder to control or optimize the property of interest. Ageneral conclusion originating from these models is that thetransition dipole moments in an excitation channel should bealigned in order to maximize the Two-Photon Absorptionprobability. The computational framework employed is responsetheory which through the response functions (linear, quadratic,cubic) offers alternative routes for evaluating the propertiesin focus; either directly and untruncated through the singleresidue of the quadratic or cubic response func- tions orthrough various schemes of truncated sum-over-statesexpressions where the key ingredients, transition dipolemoments, can be identified from the single residue of thelinear response function and double residue of the quadraticresponse function. The range of systems treated in the thesisstretches from diatomics, such as carbon monoxide and lithiumhydride, via small to large fundamental organic molecules, suchas formaldehyde, tetrazine and the trans-polyenes, to largechro- mophores, such as<i>trans</i>-stilbene, cumulenes, dithienothiophene,paracyclophane and organo-metallic systems, such as theplatinum(II)ethynyl compounds.</p>

This thesis presents time-dependent density functional theory studies on electronic and vibronically resolved linear and nonlinear optical absorption and dichroism spectra of organic molecules. Special attention has been paid to the influence of solvent environment and molecular vibrations on one-, two- and three-photon absorption and one- and two-photon circular dichroism. It is found that dielectric medium as described by polarizable continuum model can enhance remarkably three-photon absorption cross section of a highly conjugated fluorene derivative, for which the simplified two-state model is shown to be largely inadequate. Origin-invariant density functional calculations on one- and two-photon circular dichroisms of a chiral molecule confirm that the recently developed CAMB3LYP functional performs better than the popular B3LYP functional for Rydberg-states. The first experimental measurement of TPCD spectra is performed on an axial chiral system in tetrahydrofunan, where the double L-scan technique is applied. Theoretical calculations well reproduce the experimental profiles when both the electron correlation and the solvent effect are taken into account. Vibronically resolved one- and two-photon absorption spectra of charge-transfer molecules have been obtained using a Linear Coupling model, where the 'borrowing mechanism' for the so-called Herzberg-Teller contribution is analyzed in detail. It is shown that Herzberg-Teller contribution can introduce a change of sign to the chiral responses of a molecule without the involvement of different electronic states, which has important consequences for the assignment of absolute configurations of chiral molecules. Adiabatic harmonic Franck-Condon model is also applied to simulate vibronically resolved one- and two-photon circular dichroism spectra of the same chiral system, where the sign-inversion and the interference between Franck-Condon and Herzberg-Teller contributions are also observed. / QC 20100727

For the past decade, the epoxy based photoresist SU-8 has been used commercially and in the lab for fabricating micro- and nano-structures. Investigators have studied how processing parameters such as pre- and post-exposure bake temperatures affect the resolution and quality of SU-8 structures patterned using ultraviolet or x-ray lithography. Despite the advances in understanding the phenomena, not all of them have been explored, especially those that are specific to multi-photon direct laser writing (mpDLW). Unlike conventional exposure techniques, mpDLW is an inherently three-dimensional (3D) process that is activated by nonlinear absorption of light. This dissertation reports how several key processing parameters affect mpDLW using SU-8 including pre-exposure bake duration, focal depth, incident laser power, focal-point scan speed, and excitation wavelength. An examination of solvent content of films at various stages in the mpDLW by 1H-NMR shows that even moderate solvent content (over 1 wt-%) affects film viscosity and photoacid diffusion lengths, and can greatly affect the overall fidelity of small features. A study of micro-fabricated feature size versus writing depth in the material shows that even slight refractive index mismatch between SU-8 and the medium between it and the focusing objective introduces spherical aberration that distorts the focus, causing feature size to decrease or even increase in size with writing depth, depending on the average exposure power used. Proper adjustment of the average exposure power was demonstrated as a means to fabricate more uniform features with writing depth. Third, when varying the power and scan speed, it was observed that the feature-size scales with these two parameters in a manner that is consistent with a three-photon absorption mechanism at an excitation wavelength of 800 nm. When an iii excitation wavelength of 725 nm is used, the feature-size scaling becomes consistent with that of two photon absorption. This shows that the photoinitiators in the SU-8 can be activated by either two- or three-photon absorption over this wavelength range. Using an irradiance of ~2 TW cm-2 and elongated femtosecond pulses resulted in an observed fourth order power dependence. This observation is in agreement with the literature and suggests that the effective absorptive nonlinearity is also sensitive to pulse duration. These findings will be useful for creating accurate models of the process of mpDLW in SU-8. These models could be used to optimize the processing parameters and develop new processing methods and materials for high-resolution fabrication of robust 3D microstructures. Some of the findings were used to develop a method for fabricating functional microlenses on the tip of optical fibers. This approach opens a new route to functional integrated photonic devices.

No description available.

Although gold nanoparticles (GNPs) are promising probes for biological imaging because of their attracting optical properties and bio-friendly nature, properties of the multi-photon (MP) emission from GNP aggregates produced by a short-wave infrared (SWIR) laser have not been examined. In this paper, characterization of MP emission from aggregated 50 nm GNPs excited by a femtosecond (fs) laser at 1560 nm is discussed with respect to aggregate structures. The key technique in this work is single particle spectroscopy. A pattern matching technique is applied to correlate MP emission and SEM images, which includes an optimization processes to maximize cross correlation coefficients between a binary microscope image and a binary SEM image with respect to xy displacement, image rotation angle, and image magnification. Once optimization is completed, emission spots are matched to the SEM image, which clarifies GNP ordering and emission properties of each aggregate. Correlation results showed that GNP aggregates have stronger MP emission than single GNPs. By combining the pattern matching technique with spectroscopy, MP emission spectrum is characterized for each GNP aggregate. A broad spectrum in the visible region and near infrared (NIR) region is obtained from GNP dimers, unlike previously reported surface plasmon enhanced emission spectrum.

This project set out to examine the possibility that by acquiring Raman spectra and performing multi-photon imaging we can get better diagnosis and understanding of the biochemistry of an individual cancerous tumour and distinguish it from the healthy tissue. Within the frame of this study, colorectal primary and secondary cancer cells are examined with Raman spectroscopy in order to (i) study and distinguish them according to their chemical composition by applying multivariate methods and (ii) determine whether Raman spectroscopy can identify the cells which are the link between primary and secondary colorectal cancer cells, the so-called Cancer Stem Cells. The second part of this thesis is based on tissue studies. Human colorectal tissue sections are examined in a label-free manner with the use of multi-photon imaging modes (i) Two photon excitation fluorescence, (ii) stimulated Raman scattering and (iii) second harmonic generation, in order to determine whether these can provide fast and accurate diagnosis of colorectal cancer. These techniques were able to distinguish between healthy and cancerous tissue regions, based on the chemically-specific images of the tissue microenvironment and architecture. The hypothesis of Cancer stem cell is examined with the use of Raman spectroscopy shown that the CSCs have some small differences according to their tissue origin.

No description available.

No description available.

The relatively few serotonin (5-HT) neurons located in the Dorsal Raphe Nucleus (DRN) give rise to an extensive axonal network modulating a wide-range of brain functions and behaviors. In turn, the DRN receives inputs from several brain regions and therefore exhibits the characteristics of a hub network. While recent technological advancements have provided an unprecedented look at the neurobiology of the DRN, important knowledge gaps remain in understanding how the constellation of synaptic inputs to this region confers 5-HT neurons their unique coding features. As a first step towards characterizing the DRN's input processing strategy, we set out to explore the landscape of dendritic operation operating in DRN 5-HT neurons. Using multi-photon microscopy and in vitro electrophysical recordings, we conducted a morphological and electrophysiological survey of 5-HT neurons where we identified two structurally and morphologically distinct types of glutamatergic synapses both expressing small NMDAR-mediated conductance. Our initial findings provide valuable insights on local rules that govern how synaptic inputs to the DRN are being processed to ultimately confer 5-HT neurons their unique coding features.