No description available.

Thesis (Ph. D.)--Washington State University, May 2007. / Includes bibliographical references.

Thesis (Ph. D.)--Oregon State University, 2010. / Printout. Includes bibliographical references. Also available on the World Wide Web.

Thesis (Ph.D)--Physics, Georgia Institute of Technology, 2010. / Committee Chair: de Heer, Walter; Committee Member: Chou, Mei-Yin; Committee Member: First, Phillip; Committee Member: Whetten, Robert; Committee Member: Zangwill, Andrew. Part of the SMARTech Electronic Thesis and Dissertation Collection.

No description available.

I used a Mach-Zehnder atom interferometer to measure the static electric-dipole polarizabilities of K, Rb, and Cs atoms with 0.11\% uncertainty. Static polarizability measurements serve as benchmark tests for 𝑎𝑏 𝑖𝑛𝑖𝑡𝑖𝑜 atomic structure calculations. Calculating atomic properties such as polarizabilities, van der Waals coefficients, state lifetimes, or oscillator strengths involves accurately calculating the valence electrons' electric-dipole transition matrix elements. Additionally, testing Cs atomic structure calculations helps interpret the results of parity non-conservation experiments, which in turn places constraints on beyond-the-standard-model physics. I discuss improvements to our experiment that allowed us to measure static polarizabilities with 0.11% uncertainty, and we present our results in the context of recent 𝑎𝑏 𝑖𝑛𝑖𝑡𝑖𝑜 and semi-empirical static polarizabilities and recent, high-precision measurements of excited state lifetimes and van der Waals C₆ coefficients. I also used our interferometer to develop a new technique for inertial sensing. High precision, portable, atom-interferometer gyroscopes and accelerometers are desirable for self-contained inertial navigation and in the future may be used for tests of General Relativity and searches for gravitational waves using satellite-mounted inertial sensors. Satellite-mounted atom interferometers are challenging to build because of size, weight, power, and reliability constraints. Atom interferometers that use nanogratings to diffract atoms are attractive for satellite-mounted inertial sensing applications because nanogratings weigh approximately nothing and require no power. We developed a new 𝑖𝑛 𝑠𝑖𝑡𝑢 measurement technique using our nanograting atom interferometer, and we used it to measure inertial forces for the benefit of our static polarizability measurements. I also review how to calculate the sensitivity of a nanograting atom interferometer, and I employed these calculations in order to design a portable, nanograting atom interferometer inertial sensor.

Gas composition and analysis forms a large field of research whose requirements demand that measurement equipment be as affordable, uncomplicated and convenient as possible. The precise quantitative composition of an atmospheric, industrial or chemically synthesised sample of gas is of utmost importance when inferring the properties and nature of the environment from which the sample was taken, or for inferring how a prepared sample will react in its application. The most popular and widely used technique to achieve this is Gas Chromatography-Mass Spectrometry (GCMS) and, without a doubt, this technique has set the standard for gas analysis. Despite the accuracy of the GCMS technique, the equipment itself is bulky, expensive and cannot be applied readily to field work. Instead, most field work is conducted using a single gas detector, capable only of detecting one particular molecule or element at a time. Presented here is an interferometric technique that theoretically, has the ability to address all three issues of bulkiness, affordability and convenience, whilst not being limited to one particular element or molecule in its analysis. Identifying the unknown constituents of a gaseous mixture using the proposed method, employs the optical refractive properties of the mixture to determine its composition. A key aspect of this technique is that the refractive index of an arbitrary mixture of gases will vary depending on pressure and wavelength1. The Lorentz-Lorenz formula and the Sellmeier equations form the foundation of the theoretical background. The optical refractive properties of air and other atmospheric gases have been well established in the literature. The experimental investigations described here have been conducted based on this, insofar as no analysis has been conducted on gases that do not naturally occur in reasonable abundance in the atmosphere. However this does not in any way preclude the results and procedure developed from applying to a synthesised gas mixture. As mentioned, the platform of this technique relies on the pressure and wavelength dependence of the refractivity of the gas. The pressure dependence of the system is easily accounted for, in making this claim however it is still imperative the mixture be impervious to contamination from the wider atmosphere. Wavelength dependence however is perhaps slightly more difficult to accommodate. Multiple lasers, of differing wavelength form the radiative sources which underpin the method developed. Laser sources were chosen because of their coherence, making it easy to produce interference, when combined with the inherent stability of the Sagnac interferometer, provides for a very user friendly system that is able to quickly take results. The other key part of the experimental apparatus is the gas handling system, the gas(es) of interest need to be contained within an optical medium in the path of one of the beams of the interferometer. Precise manipulation of the pressure of the gas is critical in determining concentration, this has been achieved through the use of a gas syringe whose plunger is moved on a finely threaded screw, and measured on a digital manometer. The optical setup has also been explored, specifically in ruling out the use of such radiative sources as passing an incandescent source through a monochromator or the use of LED's to produce interference before settling on lasers to produce the required interference. Finally, a comprehensive theoretical background has been presented using classical electromagnetic theory as well as confirmation from a quantum perspective. The theoretical background for this study relies upon the Lorentz-Lorenz formula. It is commonly presented either from a classical or quantum perspective, in this work both classical and quantum mechanical treatments are given whilst also showing how each confirms the other. Furthermore, a thorough investigation into the dispersion functions of each of the major components of the atmosphere has been compiled from the study of refractivity on individual gases from other authors, in some cases, where no work has been done previously, this has been derived. The technique developed could be considered an ample addition to gas analysis techniques in certain circumstances in terms of expense, convenience and accuracy. The system can predict relative quantities of constituents of the atmosphere to at least 3%. The method described here would allow researchers more time to concentrate on actual results and more resources to allocate to broadening intellectual horizons. This would certainly justify further development.

<p>Utilizing a genetic algorithm training of the atom dipole interaction model was performed to arrive at C,H, N, & O atomic polarizabilities that constitute a correction to semiempirical molecular polarizability calculations increasing the accuracy of these calculations to near parity with DFT at a fraction of the computational load.</p>

Indiana University-Purdue University Indianapolis (IUPUI) / Molecular polarizability plays a significant role in chemistry, biology, and medicine. Classical prediction of polarizability often relies on atomic-type specific polarizability optimized for training set molecules, which limits the calculations to systems of similar chemical environment. Although ab initio (AI) quantum mechanical (QM) methods are more transferable in predicting molecular polarizability, their high computational costs especially when used with large basis sets for obtaining quantitatively reliable results make them less practical. To obtain accurate QM polarizability in an efficient manner, we have developed a dual-level approach, where the polarizability (α) obtained from the efficient semiempirical QM (SE) method is corrected using a set of element-base atomic polarizabilities derived from the atomic dipole interaction model (ADIM) to reproduce the density functional theory (DFT) results. We have optimized the atomic polarizability correction parameters for CHON-containing systems using a small training set of molecules and tested the resulting SE-ADIM model on the neutral drug-like molecules in the QM7B database. SE-ADIM corrected AM1 showed substantial improvement with its relative percent error (RPE) compared to B3LYP reduced from 33.81% to 3.35%. To further test its robustness for larger molecules in broader chemical bonding situations, we applied this method to a collection of drug molecules from the e-Drug3D database. For the 1004 molecules tested, our SE-ADIM model, which only contains four empirical parameters, greatly reduces the RPE in AM1 polarizability relative to B3LYP from 26.8% to 2.9%. Error decomposition shows consistent improvements across molecules with diverse bond saturations, molecular sizes, and charge states. In addition, we have applied AlphaML, a promising machine learning (ML) technique for predicting molecular polarizability, to the e-Drug3D dataset to compare its performance with our SE-ADIM correction of AM1. We found SE-ADIM performs competitively with AlphaML bolstering our confidence in the value of our method. Errors distinct to AlphaML were also discovered. We found four molecules for which AlphaML predicts negative molecular polarizabilities, all of which were peroxides. In contrast, SE-ADIM has no such issue with these molecules or this chemical type. Finally, to improve performance of SE-ADIM when correcting AM1 molecular polarizability calculations for charged molecules, we introduce a charge dependent polarizability (CDP) enabled SE-ADIM. Training the CDP enabled SE-ADIM with a single additional parameter, B, we were able to reduce error in AM1 molecular polarizability calculations of charged molecules relative to B3LYP from 29.57% to 5.16%. By contrast, SE-ADIM without CDP corrected AM1 relative to B3LYP had an RPE of 8.56%. The most benefit of CDP was evident within negatively charged molecules where AM1 error relative to B3LYP fell from 32.20% to 3.77% while SE-ADIM without CDP enabled error for these same negative molecules was 10.06%.

Neste trabalho apresentamos alguns estudos teóricos sobre propriedades eletrônicas de sistemas atômicos e moleculares em fase líquida e ambiente supercrítico. A utilização dos fluidos supercríticos têm atraído muito interesse como meio solvente para propriedades moleculares, reações químicas e são vistos como alternativa aos solventes orgânicos t´óxidos. Assim como nos solventes convencionais, descrever suas propriedades por meio de estudos em n´nível molecular tem se tornado tão interessante quanto seu uso prático. Primeiramente realizamos o estudo da polarizabilidade estática do argônio e como esta propriedade se comporta em função da variação de pressão. Fizemos também um estudo deste sistema em torno do ponto crítico e região supercrítica. Dentro do intervalo de pressão que estudamos, não observamos variações significativas na polarizabilidade, embora no regime de baixas densidades este sistema apresentou certa dependência da polarizabilidade com a densidade. Neste estudo, também calculamos a constante dielétrica no ponto crítico. Em seguida estudamos o espectro de absorção do ´átomo de xenônio em ambiente formado por argônio líquido. Nesta parte, realizamos várias simulações com o objetivo de verificar o deslocamento da linha de absorção 5p 6s deste ´átomo em relação `a densidade, explorando também as condições supercríticas. Observamos que o deslocamento do espectro ocorrido em meio solvente é para maiores energias (blue shift) `a medida que a densidade aumenta, e obtemos bom acordo com os valores medidos. Por ultimo, realizamos um estudo da mudança de um espectro eletrônico molecular onde o solvente é a ´agua supercrítica. Utilizamos a molécula paranitroanilina como sonda solvatocromica, e observamos que mesmo no regime de alta temperatura e baixa densidade ainda ocorre a formação de ligações de hidrogênio entre soluto e solvente. Obtemos um red shift para a transição eletrônica em agua supercrítica. Este resultado é medido experimentalmente tanto para ´agua em condições ambiente como em condição supercrítica, mas em ´agua supercrítica o deslocamento ´e menor. Nosso resultado para a agua supercrítica está em bom acordo com o resultado experimental e mostra que a maior contribuição para este deslocamento ´e devido ao efeito das interações eletrostáticas. Porém, ao compararmos os resultados da ´agua em condições supercríticas com as condições normais de temperatura e pressão e o dióxido de carbono supercrítico como solventes, os resultados indicam que a aproximação de incluir apenas interações eletrostáticas ´e menos satisfatória e fornece somente parte do efeito de solvente. / In this work we present some theoretical studies of the electronic properties of atomic and molecular systems in liquid and supercritical environments. The study of supercritical fluids is a interesting topic in solvent effects on molecular properties and chemical reactions. Their use can be an alternative to organic toxic solvents. Describing their molecular solvent properties, as opposite to conventional solvents, has become important as of pratical use. First we study the static polarizability of atomic argon and its behavior with pressure. The critical and near critical points also were considered in this study. In the range of pressures used, it is not observed significant changes in the polarizability, although the system present some dependence with density in the supercritical region. We have then determined the dielectric constant at the critical point. Next we study the absorption electronic spectra of xenon atom in liquid argon environment. In this part, we performed several simulations with the aim of verifying the density dependence of the spectral shift of the 5p 6s line of xenon. The supercritical region was also explored. We obtain the spectral blue shift in solvent environment for increasing density in good agreement with experiments. Finally, we study the electronic spectra of a solvatochromic probe molecule, the paranitroaniline, in supercritical water and supercritical carbon dioxide. We observe that even for high temperature hydrogen bond persists between the solute and the water molecules. A red shift in the transition of the electronic spectra of paranitroaniline is well described. This red shift is observed experimentally in water, but in supercritical water it is less pronounced. Our results for supercritical water is in good agreement with the experimental result and show that the long-range electrostatic contribution dominates the solute-solvente interaction and gives the largest influence in the calculated spectrum. Water in normal conditions and supercritical carbon dioxide were also considered for comparison and the results indicates that including only the electrostatic contribution is less satisfactory and gives only part of the total solvent effect.