This thesis is a theoretical study of the effects of vibrational degrees of freedom on the polariton physics. The work is motivated by recent experiments, which show that by allowing light to strongly couple with organic matter (inside a microcavity), polariton condensation can occur at room temperature. We begin by introducing a model, which describes localised electronic excitations of molecules coupled to cavity photon modes. The additional feature is the coupling between electronic excitations and local vibrational modes of molecules. Investigations of equilibrium phase diagrams and absorption spectra of the system (with a single cavity mode and without disorder) have revealed that coupling to vibrational modes acts to suppress the effective light-matter strength, can give rise to a sequence of normal-condensed-normal transitions as a function of temperature, and can drive the phase transition first order. We have also found that despite the vibrational sidebands existing at energies below the lower polariton, they cannot result in condensation, though their admixture has been found in the state which acquires macroscopic occupation. Secondly, we focused on the effects of excitonic disorder and the possibility of the ground state reconfiguration in ultra-strong coupling regime, with the aim to explain the temperature dependence of absorption spectra published in [A. Canaguier-Durand et al. Angew. Chem. Int. Ed. 52, 10533 (2013)]. We have found that the latter mechanism, although not impossible, could not result in any observable changes as, for the experimental parameters, it is too weak. The study of absorption spectra in the presence of disorder has revealed that the temperature dependence can be accounted for by the vibrational dressing of electronic transitions.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Physics, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / Ph.D.

A theoretical approach was developed to model the vibrational dynamics of amorphous, two-dimensional materials. The materials were modeled as continuous random networks (CRN's) comprising an assemblage of planar rings of diverse size. In-plane vibrational modes for symmetric 4-, 5-, 60, 7-, and 8-membered rings were examined. Vibrational states of isolated rings were modified by coupling the rings to a continuous network to represent rings embedded in a CRN. An effective force constant was used to couple the ring vibrations to the network's collective motions. Potentials were approximated with the use of a central force model (bond-stretching force constant) and a valence force model (bond-stretching and bond-angle-bending force constants). Valence force model calculations employed group theory. Mode frequencies were calculated using the method of small oscillations and the normal coordinate treatment. Amorphous carbon was used as a test case for the embedded ring approach. A physically consistent set of force constants for the valence force model was determined by comparing the 6-membered ring E2g mode in graphite. Frequencies for selected ring modes were calculated, resulting in a discrete line spectrum. Calculated frequencies were fitted with gaussian peaks and convoluted into theoretical spectra for comparison with the experimental Raman spectrum of amorphous carbon. Integrated gaussian lineshape intensities were assumed to be directly proportional to the CRN ring statistics. The peaks were convoluted with the peak widths, ring statistics, and number of modes as the adjustable parameters. Parameters consistent with previous research on the structure and dynamics of amorphous carbon provided satisfactory fits to the data. The best fit to the Raman data includes the E2g and A1g modes of 6-membered rings (present in Raman spectra of nanocrystalline graphite), and the Raman active E2' modes of 5- and 7-membered rings. The corresponding ring statistics agree with previous results, supporting the presence of a sizable percentage of 5- and 7- membered rings, but with no 4- or 8-membered rings. This positive result provides verification for the embedded ring approach, and supports a CRN model for amorphous carbon.

Vibrational spectroscopic imaging techniques have emerged as powerful methods of obtaining sensitive spatially resolved molecular information from microscopic samples. The data obtained from such techniques reflect the intrinsic molecular chemistry of the sample and in particular yield a wealth of information regarding functional groups which comprise the majority of important molecules found in cells and tissue. These spectroscopic imaging techniques also have the advantage of acquisition of large numbers of spectral measurements which allow statistical analysis of spectral features which are characteristic of the normal histological state as well as different pathologic disease states. Databases of large numbers of samples can be acquired and used to build model systems that can be used to predict spatial properties of unknown samples. The successful construction and application of such a model system relies on the ability to compile high-quality spectral database information on a large number of samples with minimal sample-to-sample preparation artifact. Tissue microarrays provide a consistent sample preparation for high-throughput infrared spectroscopic profiling of histologic specimens. Tissue arrays consisting of representative normal healthy prostate tissue as well as pathologic entities including prostatitis, benign prostatic hypertrophy, and prostatic adenocarcinoma were constructed and used as sample populations for infrared spectroscopic imaging at high spatial and spectral resolutions. Histological and pathological features of the imaged tissue were correlated with consecutive tissue sections stained with standard histologic stains and visualized via traditional optical microscopy and reviewed with a trained pathologist. Spectral analysis of histologic class mean spectra and subsequent cross-sample statistical validation were used to classify reliable spectral metrics for class discrimination. Multivariate Gaussian maximum likelihood classification algorithms were used to reliably classify all pixels in an image scene to one of six different histologic subclasses: epithelium, smooth muscular stroma, fibrous stroma, corpora amylacea, lymphocytic infiltration, and blood. The developed database-dependent classification methods were used as a tool to investigate subsequent microarrays designed with both normal epithelial tissue as well as adenocarcinoma from a large population of patients. Such investigation led to the identification of spectral features that proved useful in the preliminary discrimination of benign and malignant prostatic epithelial tissue.

No description available.

We study the effects of vibrations in the Pd₃ system using first-principles pseudopotential calculations. We find that upon disordering from the DO₂₂ phase, the decreases by 0.07kB. We explain our results in terms of atomic relaxations and size effects. / Singapore-MIT Alliance (SMA)

This work describes the development of a Raman spectroscopy system for measuring aerothermochemistry in high-speed jets and flames. A transmissive grating spectrometer was newly developed for capturing pure rotational Raman and rotationalvibrational Raman with a single CCD camera. Previous state-of-the-art experiments applied line imagining in known flowfields of constant pressure. The system described herein is designed to provide local measurement of pressure, with full thermochemistry, along a line. In every point, temperature will be measured by examining the Boltzmann decay of the rotational spectrum, while molar fraction will be measured from the vibrational Raman spectrum. The temperature and concentrations will then be combined to obtain partial pressure measurements via the equation of state. This work examines the phenomenology of rotational and vibrational Raman scattering and proposes algorithms that can be used for data extraction.

The generation of high-frequency current oscillations when a constant voltage is applied across an insulating tunnel gap separating two superconductors was one of the fundamental theoretical predictions made by Brian Josephson, which earned him a share of the 1973 Nobel Prize in physics. Our primary objective is to utilize superconducting transport through microscopic objects to both excite and analyze the vibrational degrees of freedom of various molecules of a biological nature. The technique stems from a Josephson junction's ability to generate radiation that falls in the terahertz gap ( 10THz) and consequently can be used to excite vibrational modes of simple and complex molecules. Analysis of the change in IV characteristics coupled with the differential conductance ( ) allows determination of both the absorption spectra and the vibrational modes of biological molecules. Presented here are both the theoretical foundations of superconductivity relevant to our experimental technique and the fabrication process of our samples. Comparisons between our technique and that of other absorption spectroscopy techniques are included as a means of providing a reference upon which to judge the merits of our novel procedure. This technique is meant to improve not only our understanding of the vibrational degrees of freedom of useful biological molecules, but also these molecule's structural, electronic and mechanical properties.

The work presented in this thesis was motivated by the large amount of experimental investigations of the phonons in quasicrystals. The generalized vibrational density of states (GVDOS) was measured for many quasicrystalline phases and in some cases at different temperatures [suck et al (1997), Dugain et al (1997)]. The progress achieved in the structure determination of approximants to some quasicrystals was a legitimate motivation for numerical investigations of lattice dynamics in these structures. Two different types of interatomic interactions were used: the spring model and the ab-initio pair potentials. The investigations explained the shape of some experimentally measured GVDOS (d-AlNiCo, o-Al13Co4 and i-ZnMgY) via the calculation of the partial vibrational densities of states. Both calculated and measured GVDOS of the d-AlNiCo phase showed an intensity excess at low energies relatively to the ideal Debye behaviour. This excess was found to be a consequence of the existence of special modes at theses energies which are called ``quasi-localized modes''. These modes seem to be characteristic of the lattice dynamics in the complex Al-TM structures. To calculate the frequency shift due to the shift of the GVDOS through low energies observed experimentally at high temperatures, a new method based on a Monte-Carlo simulation was developed. It was shown that the quasi-localized modes introduce large frequency shifts at low energies. Finally, the vibrational entropy was also investigated, and it was found that it contributes to the stabilization of the complex structures over the relatively simple structures at high temperatures. / Die Arbeit, die in dieser Dissertation präsentiert wird, wurde durch eine Vielzahl von experimentellen Beobachtungen von Phononen in Quasikristallen motiviert. Die verallgemeinerte vibrationelle Zustandsdichte (GVDOS, generalized vibrational density of states) wurde für viele quasikristalline Phasen gemessen und für einige auch bei verschiedener Temperatur [Suck et al. (1997), Dugain et al. (1997)]. Der Fortschritt, der in der Bestimmung von Näherungen für einige Quasikristalle erreicht wurde war eine legitime Motivation für numerische Untersuchungen der Gitterdynamik auf diesen Strukturen. Es wurden zwei unterschiedliche interatomare Wechselwirkungen verwendet: Das Federmodell und die ab-initio Paar Potentiale. Die Untersuchungen erklärten die Form einiger experimenteller GVDOS-Messungen (d-AlNiCo, o-Al13Co4 und i-ZnMgY) mittels der Berechnung der partiellen vibrationellen Zustandsdichte. Beide, berechnete und gemessene, GVDOS der d-AlNiCo Phase zeigten einen Intensitätsanstieg bei kleinen Energien relativ zum idealen Debye Verhalten. Dieser Anstieg stellte sich als Konsequenz der Existenz von besonderen Moden bei diesen Energien heraus, die quasi-lokalisierte Moden genannt werden. Diese Moden scheinen charakteristisch für die Gitterdynamik in den komplexen Al-TM Strukturen zu sein. Um die experimentell beobachtete Frequenzverschiebung aufgrund der Verschiebung der GVDOS durch niedrige Energien zu berechnen, wurde eine neue, auf Monte-Carlo Simulation beruhende, Methode entwickelt. Es wurde gezeigt, daß die quasi-lokalisierten Moden große Frequenzverschiebungen bei kleinen Energien hervorrufen. Letzt-lich wurde auch die vibrationelle Entropie untersucht und es stellte sich heraus, daß sie bei hohen Temperaturen dazu beiträgt die komplexen Strukturen gegenüber den relativ einfachen zu stabilisieren.

Rozprawa habilitacyjna--University of Warsaw. / Bibliography: p. [146]-155.