The electronic state ordering is calculated in substituted meta-xylylene diradicals for reproduction and comparison of results previously published by other authors. The second hyperpolarizability, γ, is calculated in the same systems using different methods. The diradical character is calculated for comparison and discussion of the γ values. The obtained electronic state ordering agrees qualitatively with previous findings. The γ values obtained from the finite-field method, which are related to the diradical character, agree with theory. The γ values obtained from the sum-over-states method, which relate to the vertical state ordering, are unsatisfactory.

Supercontinuum (SC) generation, oftentimes referred to as white-light continuum (WLC), has been a subject of interest for more than 40 years. From the first observation of WLC in condensed media in the early 1970s to the first observation of WLC in gases in the mid-1980s, much work has been devoted to developing a framework for understanding the complex nature of this phenomenon as well as discovering its utility in various applications. The main effort of this dissertation is to develop a WLC for the purpose of broadband nonlinear spectroscopy and use it in spectroscopic measurements. The ability to generate a high-quality, high-spectral-irradiance source of radiation confined in a single beam that spans the visible and near-infrared spectral regimes has great utility for nonlinear measurement methods such as the Z-scan technique. Using a broadband WLC instead of conventional tunable sources of radiation such as optical parametric generators/amplifiers has been shown to increase the efficiency of such measurements by nearly an order of magnitude. Although WLC generation has many complex processes involved, and complete models of the process involve highly complex numerical modeling, simple models can still guide us in the optimization of systems for WLC generation. In this dissertation the effects of two key mechanisms behind WLC generation in gaseous media are explored: self-phase modulation (SPM) and ionization leading to plasma production. The effects of SPM are largely dependent upon the third-order nonlinear refractive index, n2, of the gaseous medium whereas the effects of plasma production are dependent upon many parameters including the initial number density, ionization potential/energy, and the rate of ionization production. It is found that in order to generate a stable WLC suitable for nonlinear spectroscopy, the phase contributions from SPM and plasma production should be nearly equal. This guided our experiments in inert gases using mJ level, 150 fs-FWHM (full-width at half-maximum) pulses at 780 nm as well as 40 fs-FWHM pulses primarily at 1800 nm to create a stable, high-spectral-irradiance WLC. The generated WLC is shown to have sufficient spectral energy and spatial quality suitable for nonlinear spectroscopic measurements. In addition to extending the WLC bandwidth by using a long wavelength (1800 nm) pump source, it is found that by using a secondary weak seed pulse with a peak irradiance three orders of magnitude less than the main pulse, the spectral energy density is enhanced by more than a factor of 3 in Krypton gas for a WLC spectrum that spans over 2 octaves. Numerical simulations are presented which qualitatively describe the experimental results. The spectral enhancement of the WLC by seeding is also demonstrated for other inert gases and condensed media. Other efforts described in this dissertation include the development of the Dual-Arm Z-scan technique and its extension to measuring thin film nonlinearities in the presence of large substrate signals as well as predicting the n2 spectra of organic molecules (where we can approximate their behavior as if they were centrosymmetric) from knowledge of the one-photon and two-photon absorption spectra using a simplified sum-over-states quantum perturbative model by utilizing a quasi 3-level and quasi 4-level system.

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Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.