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The aim of this project was to study what mixed cluster fragments were formed in the interaction between radiation and H2O-CO2 clusters formed by adiabatic expansion, both experimentally and using simulations. The experiment was done using a mass spectrometer at the MAX IV synchrotron facility and by studying the time-of-flight of the ionic fragments. All peaks in the mass spectrum were identified by converting the time-of-flight to mass/charge, and the spectrum for two different photon energies (307 eV and 550 eV ) and two different stagnation pressures (1.5 bar and 2.2 bar) were compared. The data showed that mixed clusters were formed, including fragments with extra hydrogen atoms. The mass spectra showed a larger change in peak height and width with increasing pressure than with increasing photon energy. Molecular dynamics simulations were used to study the stability of the identified clusters. The simulated clusters contained CO2, H2O and H2O+. As a measure of stability, the largest centre of mass distance between the H2O+ molecule and any other molecule in the cluster in every time step of the simulation was determined. The structure of the more stable clusters was also studied visually. The simulations showed that the clusters vary greatly in stability, but generally clusters with many H2O molecules were more stable. The stable structures had the H2O+ molecule on one end of the cluster, with its hydrogen atoms directed towards the rest of the molecules. Although the clusters with many H2O molecules were more stable in the simulations, clusters with many CO2 molecules were more abundant in the experimental data. This was most likely due to a high amount of CO2 in the gas used to create the clusters. / Målet med projektet var att experimentellt och med simuleringar studera de klusterfragment som bildas i interaktionen mellan strålning och blandade H2O-CO2-kluster skapade genom adiabatisk expansion. I experimentet studerades flygtiden hos de laddade fragmenten genom mätningar med en masspektrometer vid synkrotronanläggningen MAX IV. Topparna i masspektrumet identifierades genom att konvertera flygtiden till massa/laddning. Två olika strålenergier (307 eV och 550 eV) samt två stagnationstryck (1.5 bar och 2.2 bar) jämfördes. Datan visade att blandade kluster bildades, bland annat identifierades fragment med extra väteatomer. Skillnaden i spektrumen var större mellan de olika trycken än mellan de olika energierna, framför allt så producerade det högre trycket fler och större klusterfragment. Molekyldynamiksimuleringar användes för att undersöka stabiliteten hos de identifierade klustren. De kluster som simulerades innehöll CO2, H2O och H2O+. För att mäta stabiliteten av klustren bestämdes det största avståndet mellan H2O+ molekylen och någon annan molekyl i klustret i varje tidssteg av simuleringen. Strukturen hos de mer stabila klustern undersöktes också visuellt. Simuleringarna visade att stabiliteten hos klustren varierade mycket, men generellt så var kluster med många H2O molekyler mer stabila. I de stabila klusterstrukturerna var H2O+ molekylen placerad på kanten av klustret, med dess väteatomer riktade mot resterande molekyler. Kluster med många H2O molekyler var mer stabila i simuleringarna, men experimentellt förekom fler kluster med många CO2 molekyler. Detta beror troligtvis på att gasen som användes för att skapa klustren till stor del bestod av CO2 gas.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25301号 / 工博第5260号 / 新制||工||2001(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 作花 哲夫, 教授 安部 武志, 教授 佐藤 啓文 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Abstract In this work, evolution of structural properties of anhydrous and hydrated alkali halide clusters are studied using synchrotron radiation based photoelectron spectroscopy. Alkali metal core level spectra of small anhydrous RbCl, RbBr, CsCl and CsBr clusters indicate a NaCl structure. For larger CsBr clusters a structural phase transition to CsCl structure is likely the case. Alkali halide core level spectra of mixed RbBr-water clusters indicate that at dilute concentration the salt is dissolved by the water cluster but ion pairing increases with concentration. Modeling of gas phase cluster formation and electronic structure calculations of core level chemical shifts are used to interpret the experimental spectra.

Devido à inconfiabilidade do modelo EM-X?, no cálculo da energia total, consideramos uma correção na densidade de carga \"muffin-tin\". Com esta correção podemos ajustar a energia total, a partir de parâmetros definidos na teoria. O objetivo deste trabalho é o estudo da curva da energia total associada ao estado excitado do sistema GaAs: AsGa, quando o átomo substitucional de As se desloca na direção . Partindo de cálculos de primeiros princípios (LARGE UNIT CELL APPROACH), reproduzimos a curva da energia total do estado fundamental. A partir dos parâmetros encontrados na correção não \"muffin-tin\" da densidade de carga, calculamos a curva do estado excitado utilizando o conceito de estado de transição de Slater. Nossos resultados mostraram que o efeito Jahn-TeIler não ocorre para defeitos tipo antisítio. Vimos também que a curva do comportamento dos autovalores com o deslocamento do átomo substitucional, está de acordo com cálculos recentes encontrados na literatura. / Since total energy calculations within the Multiple Scattering-X? model are not reliable, a non \"muffin-tin\" correction to the charge density has been considered. With this correction the total energy can be adjusted through parameters defined in the theory. The aim of this work is to study the total energy curve of the excited state of the GaAs: AsGa system when the arsenic substitutional atom is displaced in the direction. As a first step, the ground-state total energy curve obtained from first-principles calculations (LARGE UNIT CELL APPROACH) was reproduced. From the parameters found for the non \"muffin-tin\" charge density corrections, we have calculated the excited-state total energy curve by using the Slater transition-state concept. Our results show that the Jahn-Teller effect is not expected to occur for antisite-like defects. Moreover, the obtained behavior of the eigenvalues with displacement of the substitutional atom is in fairly good agreement with recent theoretical calculations found in the literature.

Devido à inconfiabilidade do modelo EM-X?, no cálculo da energia total, consideramos uma correção na densidade de carga \"muffin-tin\". Com esta correção podemos ajustar a energia total, a partir de parâmetros definidos na teoria. O objetivo deste trabalho é o estudo da curva da energia total associada ao estado excitado do sistema GaAs: AsGa, quando o átomo substitucional de As se desloca na direção . Partindo de cálculos de primeiros princípios (LARGE UNIT CELL APPROACH), reproduzimos a curva da energia total do estado fundamental. A partir dos parâmetros encontrados na correção não \"muffin-tin\" da densidade de carga, calculamos a curva do estado excitado utilizando o conceito de estado de transição de Slater. Nossos resultados mostraram que o efeito Jahn-TeIler não ocorre para defeitos tipo antisítio. Vimos também que a curva do comportamento dos autovalores com o deslocamento do átomo substitucional, está de acordo com cálculos recentes encontrados na literatura. / Since total energy calculations within the Multiple Scattering-X? model are not reliable, a non \"muffin-tin\" correction to the charge density has been considered. With this correction the total energy can be adjusted through parameters defined in the theory. The aim of this work is to study the total energy curve of the excited state of the GaAs: AsGa system when the arsenic substitutional atom is displaced in the direction. As a first step, the ground-state total energy curve obtained from first-principles calculations (LARGE UNIT CELL APPROACH) was reproduced. From the parameters found for the non \"muffin-tin\" charge density corrections, we have calculated the excited-state total energy curve by using the Slater transition-state concept. Our results show that the Jahn-Teller effect is not expected to occur for antisite-like defects. Moreover, the obtained behavior of the eigenvalues with displacement of the substitutional atom is in fairly good agreement with recent theoretical calculations found in the literature.

Les radiations peuvent endommager notre environnement biologique mais elles peuvent aussi être bienfaisantes si elles sont contrôlées. L'action initiale des radiations à l'échelle microscopique consiste en une excitation électronique dans une molécule. L'observation de la redistribution de l'énergie dans l'environnement de cette molécule excitée est primordiale à la compréhension et à la description de l'effet des rayonnements dans les systèmes biomoléculaires. Les agrégats de molécules isolés en phase gazeuse constituent des systèmes modèles prometteurs pour étudier les interactions entre molécules sous irradiation. La première partie de ce travail décrit la construction et la validation d'une ligne de faisceau permettant la production de paquets d'agrégats moléculaires froid injectables dans l'anneau de stockage RICE à RIKEN. La ligne de faisceau est composée d'une source electrospray, d'un filtre en masse quadripolaire, de guides d'ions d'un tube d'accélération, la pièce centrale étant un piège à ions cryogénique refroidi à 4 K. Le paquet d'ions froids, dont les ions ont été sélectionnés en masse et accélérés jusqu'à 20 keV, a été sondé avec un laser. La ligne a été validée par la mesure d'un spectre d'action du bleu de méthylène. La seconde partie de ce travail s'appuie sur les expériences réalisées auprès du dispositif d'irradiation d'agrégats moléculaires (DIAM-IPNL). La méthode COINTOF-VMI permet la mesure de la distribution de vitesse des molécules d'eau évaporées à partir d'un agrégat après collision à haute vitesse avec un atome d'argon. Les distributions de vitesse mesurées pour des agrégats mixtes pyridine protonée et eau présentent deux composantes : une partie à basse vitesse qui correspond à une évaporation après redistribution de l'énergie dans l'agrégat, et une partie à haute vitesse où la molécule d'eau est évaporée avant redistribution de l'énergie. La comparaison des résultats avec les distributions calculées par dynamique moléculaire statistique montre que la partie basse vitesse peut être interprétée comme la contribution des deux possibilités d'excitation induites par la collision : l'excitation de la pyridine protonée ou l'excitation d'une des molécules d'eau / Radiation can damage our biological environment, but it can also be beneficial under certain controlled conditions. Initial action at microscopic scale consists of electronic excitation in molecules. The redistribution of this excitation energy to the environment is the primary process to be understood to describe the radiation effect on biomolecular system. Isolated molecular clusters in gas-phase are a promising model system to study the molecular interaction under radiation.The first part of this work describes the construction and the validation of a beamline which can produce bunches of cold molecular cluster ions to be injected in the RIKEN cryogenic electrostatic (RICE} storage ring. The beamline is composed of an electrospray ion source, a quadrupole mass filter, ion guides and an acceleration tube; with the main part being a cryogenic ion trap cool down to SK. The cold ion bunches, in which the ions have been mass selected and accelerated to 20keV, was probed with a laser. The beamline was successfully taken into operation and a measurement of the methylene blue action spectrum in gas-phase was carried out. The second part of this work rely on experiment realized with the dispositif d'irradiation d'agrégats moléculaires (DIAM-IPNL}. The COINTOF-VMI method allows the measurement of the velocity distributions of evaporated molecules from a cluster after high velocity collisions with an argon atom. The velocity distribution measured for mixed clusters protonated pyridine and water has two components: a low velocity part which corresponds to the evaporation of a water molecule after energy redistribution in the cluster, and a high velocity part in which the molecule is evaporated before total energy redistribution. Comparison with the distribution calculated by statistic molecular dynamic simulation shows that the low velocity part can be interpreted as the contribution of two possible excitations induced by collision: excitation on protonated pyridine and excitation on a water molecule