No description available.

No description available.

No description available.

Thesis (M.S.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on November 11, 2008) Includes bibliographical references.

Diss.--Eidgenössische technische hochschule. / "Diss. no. 4611." Includes biography.

Diss.--Eidgenössische technische hochschule. / "Diss. no. 4611." Includes biography.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1983. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1966. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

In the past two decades, a number of artificial molecular motors have been constructed using organic molecules as components which can perform unidirectional motion. Among the best-known examples are the light-activated molecular rotary motors synthesized and analyzed in B. L. Feringa's lab. Yet there is limited understanding of the photoisomerization and thermal isomerization processes that control the speed and energy conversion efficiency of these molecular devices. The present thesis work aims at: 1) developing a computational methodology to provide the atomic and electronic details that allow for quantitative descriptions of light-activated molecular motion, 2) improving the understanding of the physical principles governing photo- and thermal-isomerization processes in specific molecular systems, and 3) proposing a new strategy of molecule design to assist experimental investigations. A key component in our methodology is the calculation of the potential energy surface (PES) spanned by collective atomic coordinates using ab initio quantum mechanical methods. This is done both for the electronic ground state, which is relatively straightforward, and for the photo-excited state, which is more involved. Once the PES is known, classical statistical mechanical methods can be used to analyze the dynamics of the slow variables from which information about the rotational motion can be extracted. Calculation of the PES is computationally expensive if one were to sample the very high dimensional space of the atomic coordinates. A new method, based on the torque experienced by individual atoms, is developed to capture key aspects of the intramolecular relaxation in terms of angular variables associated with the rotational degrees of freedom. The effectiveness of the approach is tested on specific light-driven molecular rotary motors that were successfully synthesized and analyzed in previous experiments. Finally, based on the experience accumulated in this study, a new molecular rotary motor driven by visible light is proposed to reach MHz rotational frequency.

Infrared absorption spectra of HC1 and HBr, suspended in solid argon, krypton and nitrogen, were recorded in order to obtain information on intermolecular forces. SO₂ in argon and nitrogen, and CO in argon were also studied. The spectra were observed in the temperature range from liquid helium temperatures up to the melting point of the matrix. The halogen acids gave more complicated spectra in the noble gas matrices than in nitrogen. This has been correlated with the different thermal properties of the matrix materials. Matrix to solute ratios from 100 to 800 to 1 were used and evidence was found for solute-solute interactions, arising from incomplete isolation of solute molecules at the lower ratios. During the warm-up period at the end of an experiment, additional peaks appeared in the spectra. It is suggested that these new peaks were due to clusters of solute molecules produced by diffusion of the solute through the lattice. Semi-empirical calculations were carried out to estimate shifts of vibrational frequencies of the trapped molecules. From these calculations it was concluded that repulsive intermolecular forces play an important part in determining the magnitude, and direction of the shifts. A first order perturbation calculation was made, using a Lennard-Jones' potential, to determine the effect of the matrix on the rotational energy levels of a trapped molecule. Spectra of the clathrate-hydrates of SO₂, H₂S and krypton were recorded at liquid nitrogen temperatures, and the SO₂ hydrate was studied in the temperature range from 4° to 120° K. The spectrum of the water skeletal vibrations exhibited several interesting features. The assignment of the 1600 cmˉ¹ and 2200 cmˉ¹ peaks to v₂ and v₂ + vR was confirmed and a new peak at 2410 cmˉ¹ was observed. A lattice mode in the spectrum of the S0₂ hydrate was observed in combination with V₃ of SO₂. / Science, Faculty of / Chemistry, Department of / Graduate