<p> The infrared and Raman spectra of cyanoacetylene and deuterocyanoacetylene have been measured and ground state vibrational energy levels have been obtained from the analysis of these spectra.</p> <p> Two band systems have been identified in the absorption spectrum of cyanoacetylene in the region 2700 - 2000 Å. Vibrational and rotational analyses have shown that the lower energy transition involves a non-linear planar upper state having A" symmetry. Approximate geometry of the molecule in the A" state has been determined.</p> <p> In the second electronic transition the upper state has been found to be linear. A vibrational analysis has been obtained on the basis of an electronically forbidden 1Δ<--- 1 Σ+ or 1 Σ- <--- 1 Σ+ transition, which is made allowed by vibronic interactions.</p> / Thesis / Doctor of Philosophy (PhD)

<p> An experimental study of vibrational energy transfer in ortho and para NH3(v2) is presented. The vibrational relaxation rates are necessary to characterize mid-IR pulsed and cw NH3 lasers, and the interpretation of these rates is of theoretical importance. Accurate information on the (V-T) process in NH3/N2 mixtures and the (V-V) energy transfer between ortho and para 15NH3 and 14NH3 is now available. </p> <p> First, NH 3 linestrengths and linewidths were accurately measured with a tunable diode laser (TDL) so that ammonia concentrations could be calculated from TDL scans. The energy transfer mechanisms were studied by exciting the v2 vibration of NH3 with a Q-switched cO2 laser and probing the subsequent changes in population with a TDL. A difference in v 2 lifetimes was observed between ortho and para NH3 transitions, and is explained by a (V-V) transfer of energy between the NH3 species. An isolated ortho 15NH3 absorption line was pumped and vibrational transfer of energy was observed to ortho and para 14NH3 and 15NH3. </p> / Thesis / Master of Science (MSc)

<p> The infrared and Raman spectra of ethynylbenzene-h6, -d1, -d5 and -d6 have been analysed, and the fundamental frequencies assigned.</p> <p> Vibrational analyses of the electronic spectra of ethynylbenzene-h6, -d1, -d5 and -d6 in the 2900-2500 Å region have been carried out. The transition is identified as an allowed A~1B2<--X~1A1 transition. A very strong "forbidden" component, which borrows intensity from a B~1A1<--X~1A1 transition by vibronic interactions, also appears in the spectrum.</p> <p> Semi-empirical LCAO-SCF-MO-CI calculations predict the lowest singlet excited state to be of B2 symmetry, at an energy above the ground state close to the experimental values.</p> <p> Rotational band contour analysis substantiates the observation that both A- and B-type bands are present in the electronic spectrum. Ethynylbenzene remains planar and shows little geometrical change on electronic excitation.</p> / Thesis / Doctor of Philosophy (PhD)

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Control of underactuated mechanical systems is of interest as it allows for control authority over all of a system's degrees of freedom without requiring actuation of the full system. In addition to this, open-loop control of a system provides the advantage of applying to systems with unmeasurable states or where sensor integration is not feasible. Vibrational control is an open-loop control strategy that uses high-frequency, high-amplitude forcing to control underactuated mechanical systems. This thesis is concerned with exploring two underactuated mechanical systems that are controlled using vibrational inputs. The first system, a 3 degrees of freedom (DOFs) 2-link mechanism with 1 actuated DOF which is an example of a vibrational control system with 1 input and 2 unactuated DOFs, is used to review analytical results of stability analysis using the averaged potential. Theoretical and numerical results are presented for the achievable stable configurations of the system and the effects of changing the physical parameters on the achievable stable configurations are studied. The primary contribution of this effort is the development of an experimental apparatus where vibrational control is implemented. The second system is a 4DOF system composed of a 2DOF spherical pendulum supported by an actuated 2DOF cart used to study the effects of multiple vibrational inputs acting on a system. Theoretical and numerical analysis results are presented for three variants of harmonic forcing applied to the two actuated degrees of freedom: 1) identical input waveforms, except for the amplitudes, 2) identical input waveforms, except for the amplitudes and a phase shift, and 3) identical input waveforms, but at different frequencies and amplitudes. The equilibrium sets under open-loop vibrational forcing are determined for all three cases. A general closed-loop vibrational control scheme is presented using proportional feedback of the unactuated coordinates superposed with the zero-mean, $T$-periodic vibrational input. / M.S. / Underactuated mechanical systems are systems where the driven degrees of freedom are fewer than the total degrees of freedom of the system. These systems can be controlled using vibrational control which is an open-loop control strategy that uses high-frequency, high-amplitude forcing to control the states of a system. An open-loop control strategy is one in which there are no measurements of the system states required in the control scheme. This allows for control of systems where sensor integration is not feasible. This thesis is concerned with exploring vibrational control of two underactuated mechanical systems. The stability of the equilibrium sets of these systems is assessed using the averaged potential, which is an energy-like quantity used to determine stability of equilibria of systems with high-frequency inputs. Theoretical and numerical results are presented for both systems and the effects of physical parameters and variants of harmonic forcing on the achievable stable configurations of the systems are studied. The two main contributions of the thesis are the development of an experimental apparatus where vibrational control is physically implemented for one system and the outline of the closed-loop vibrational control scheme.