This thesis reports the use of both dc and ac electric fi eld induced resonant energy transfer, RET, between cold Rydberg atoms as a useful tool for enhancement of interatomic interactions. A general technique for laser frequency stabilization and its suitability for Rydberg atom excitation is also demonstrated. RET between cold Rydberg atoms was used to determine Rydberg atom energy levels. The ⁸⁵Rb atoms are laser cooled and trapped in a magneto-optical trap. For energy level determination experiment, atoms were optically excited to 32d₅/₂ Rydberg states. The two-atom process 32d₅/₂ + 32d₅/₂ → 34p₃/₂+30g is resonant at an electric fi eld of approximately 0.3 V/cm through dipole dipole interaction. The experimentally observed resonant fi eld, together with the Stark map calculation is used to make a determination of the ⁸⁵Rb ng-series quantum defect to be ⵒg(n = 30) = 0.00405(6). The ac Stark eff ect was also used to induce RET between cold Rydberg atoms. When a 28.5 GHz dressing field was set at speci fic fi eld strengths, the two-atom dipole-dipole process 43d₅/₂ + 43d₅/₂ → 45p₃/₂ + 41f was dramatically enhanced, due to induced degeneracy of the initial and final states. This method for enhancing interactions is complementary to dc electric- field-induced RET, but has more flexibility due to the possibility of varying the applied frequency. At a dressing field of 28.5 GHz all of the participating levels (43d₅/₂, 45p₃/₂ and 41f) show signi cant shifts and these give a complicated series of resonances. An oscillating electric fi eld at 1.356 GHz was also used to promote the above RET process where the atoms are initially excited to the 43d₅/₂ Rydberg states. The ac fi eld strength was scanned to collect RET spectra. Di fferent resonances were observed for diff erent magnetic sublevels involved in the process. Compared to the higher dressing field frequency of 28.5 GHz, the choice of dressing frequency of 1.356 GHz, which is slightly blue detuned from the 41f - 41g transition, and structure of the spectra may be understood, by analogy with the dc field case.

The studies presented in this thesis explore electronic energy transfer (EET) in light-harvesting antenna complexes and investigate the role of quantum coherence in EET. The dynamics of energy transfer are investigated in three distinct length scales and a different formulation of the exciton transport problem is applied at each scale. These scales include: the scale of a molecular dimer, the scale of a single protein and the scale of a molecular aggregate. The antenna protein phycoerythrin 545 (PE545) isolated from the photosynthetic cryptophyte algae Rhodomonas CS4 is specifically studied in two chapters of this thesis. It is found that formation of small aggregates delocalizes the excitation across chromophores of adjacent proteins, and that this delocalization has a dramatic effect in enhancing the rate of energy transfer between pigments. Furthermore, we investigate EET from a donor to an acceptor via an intermediate site and observe that interference of coherent pathways gives a finite correction to the transfer rate that is sensitively dependent on the nature of the vibrational interactions in the system. The statistical fluctuations of a system exhibiting EET are investigated in the final chapter. The techniques of non-equilibrium statistical mechanics are applied to investigate the steady-state of a typical system exhibiting EET that is perturbed out of equilibrium due to its interaction with a fluctuating bath.

The studies presented in this thesis explore electronic energy transfer (EET) in light-harvesting antenna complexes and investigate the role of quantum coherence in EET. The dynamics of energy transfer are investigated in three distinct length scales and a different formulation of the exciton transport problem is applied at each scale. These scales include: the scale of a molecular dimer, the scale of a single protein and the scale of a molecular aggregate. The antenna protein phycoerythrin 545 (PE545) isolated from the photosynthetic cryptophyte algae Rhodomonas CS4 is specifically studied in two chapters of this thesis. It is found that formation of small aggregates delocalizes the excitation across chromophores of adjacent proteins, and that this delocalization has a dramatic effect in enhancing the rate of energy transfer between pigments. Furthermore, we investigate EET from a donor to an acceptor via an intermediate site and observe that interference of coherent pathways gives a finite correction to the transfer rate that is sensitively dependent on the nature of the vibrational interactions in the system. The statistical fluctuations of a system exhibiting EET are investigated in the final chapter. The techniques of non-equilibrium statistical mechanics are applied to investigate the steady-state of a typical system exhibiting EET that is perturbed out of equilibrium due to its interaction with a fluctuating bath.

No description available.

A continuous wave infrared CO laser has been used to monitor kinetic processes occurring behind shock waves. Studies have been made of both vibrational energy transfer and reaction kinetics. It has been demonstrated that, following shock-heating, the vibrational levels of CO and DC1 relax via a continuous series of Boltzmann distributions into the final Boltzmann equilibrium distribution at rhe translational temperature. This is shown to be in accord with the established theory, and it is proposed that all diatomic molecules relax in this manner. Previous results for HI, which suggested otherwise, are questioned, and the theoretical arguments used to explain these results are shown to be misconceived. A new method is developed to calculate vibrational relaxation times from any laser absorption trace. The initial vibrational distribution of CO formed in the unimolecular decomposition of OCS at 4000 K has been investigated. It has been found that at least 90 % of the CO is born in the lowest vibrational level v=0, when 50 % would be in v=0 at equilibrium. This result is explained in terms of the dynamics of the reaction. The kinetics of the isotope exchange reaction ¹²C¹⁸O + ¹³C<sup>16>O ⥋ ¹²C¹⁶O + ¹³C¹⁸O have been investigated. The results have been shown to be consistent with an atomic chain mechanism, in conflict with the conclusions of earlier work. Reasons for this are discussed. A general account of the principles of operation of the apparatus is given, and conclusions are arrived at for the most profitable directions of future work.

The emerging field of nanotechnology, which spans diverse areas such as nanoelectronics, medicine, chemical and pharmaceutical industries, biotechnology and computation, focuses on the development of devices whose improved performance is based on the utilization of self-assembled nanoscale components exhibiting unique properties owing to their miniaturized dimensions. The first phase in the conception of such multifunctional devices based on integrated technologies requires the study of basic principles behind the functional mechanism of nanoscale components, which could originate from individual nanoobjects or result as a collective behaviour of miniaturized unit structures. The comprehensive studies presented in this thesis encompass the mechanical, dynamical and photophysical aspects of three nanoscale systems. A newly developed europium sulfide nanocrystalline material is introduced. Advances in synthetic methods allowed for shape control of surface-functionalized EuS nanocrystals and the fabrication of multifunctional EuS-CdSe hybrid particles, whose unique structural and optical properties hold promise as useful attributes of integrated materials in developing technologies. A comprehensive study based on a new class of multifunctional nanomaterials, derived from the basic unit of barcoded metal nanorods is presented. Their chemical composition affords them the ability to undergo autonomous motion in the presence of a suitable fuel. The nature of their chemically powered self-propulsion locomotion was investigated, and plausible mechanisms for various motility modes were presented. Furthermore functionalization of striped metallic nanorods has been realized through the incorporation of chemically controlled flexible hinges displaying bendable properties. The structural aspect of the light harvesting machinery of a photosynthetic cryptophyte alga, Rhodomonas CS24, and the mobility of the antenna protein, PE545, in vivo were investigated. Information obtained through a combination of steady-state and time-resolved spectroscopy in conjunction with quantum chemical calculations aided in the elucidation of the dynamics and the mechanism of light harvesting in the multichromophoric phycobiliprotein phycocyanin PC645 in vitro. Investigation of the light-harvesting efficiency and optimization of energy transfer with respect to the structural organization of light-harvesting chromophores on the nanoscale, can provide us with fundamental information necessary for the development of synthetic light-harvesting devices capable of mimicking the efficiency of the natural system.

No description available.

Thesis (M.S.)--University of Missouri--Rolla, 2007. / Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed December 11, 2007) Includes bibliographical references.

Thesis (Ph.D.)--University of Western Australia, 2007.

Thesis (Ph.D.) - University of St Andrews, May 2008.