Thesis (Ph. D.)--University of Wisconsin--Madison, 1980. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 161-165).

No description available.

A systematic study of the change in proton single-particle occupancies in two neutrinoless double beta decay candidates, 130Te to 130Xe and 136Xe to 136Ba, has been performed. Final states in 129Sb, 129I, 135I and 135Cs have been populated using the (d,3He) single proton removal reaction. The deuterons were accelerated to 101 MeV using the coupled azimuthally varying field and Ring cyclotrons at the Research Center for Nuclear Physics, University of Osaka. The outgoing ejectiles were momentum analysed using the Grand Raiden magnetic spectrometer. Absolute cross sections were measured for states up to 7 MeV in excitation. Transferred angular momenta were identified through a comparison of angular distributions with those calculated using the distorted-wave Born approximation. Spectroscopic factors were extracted from the experimental cross sections. In addition to the 0v2B decay candidates the reaction was also performed on 128Te, 132Xe, 134Xe and 138Ba as a consistency check. The occupancies of the nuclei were determined from the spectroscopic factors, the reaction model was normalised using a common normalisation factor across all targets. The change in occupancies between the 0v2B decay candidates and their daughters were then determined. The change in occupancies were then compared with those calculated by interacting shell model, interacting boson model and quasiparticle random phase approximation. This comparison showed that whilst the three theories were qualitatively able to reproduce the change in occupancies, quantitatively there are significant discrepancies. These are the same models that are used to determine the nuclear matrix elements governing the rate of 0v2B decay.

The formation of base pair radical anions and cations is closely related to many fascinating research fields in biology and chemistry such as genetic mutation, radiation-induced DNA damage and dynamics of charge transfer in DNA. However, the relevant knowledge so far mainly comes from studies on isolated base pair radical anions and cations, and their behavior in the DNA environment is less understood. In this study, we focus on how the nucleobase sequence affects the properties of the guanine¡Vcytosine (G:C) base pair radical anion and cation. The energetic barrier and reaction energy for the proton transfer along the N1(G)¡VH¡E¡E¡EN3(C) hydrogen bond and the stability of (G:C)¡E (i.e., electron affinity and ionization potential of G:C) embedded in different sequences of base-pair trimer were evaluated using density functional theory and two-layer ONIOM method. The computational results demonstrated that the presence of neighboring base pairs has an important influence on the behavior of (G:C)¡E in the gas phase. The excess electron and positive hole were found to be localized on the embedded G:C and the charge leakage to neighboring base pairs was very minor in all of the investigated sequences. Accordingly, the sequence behavior of the proton transfer reaction and the stability of (G:C)¡E is chiefly governed by electrostatic interactions with adjacent base pairs. However, the effect of base stacking, due to its electrostatic nature, is severely screened upon hydration, and thus, the sequence dependence of the properties of (G:C)¡E in aqueous environment becomes relatively weak and less than that observed in the gas phase. The effect of geometry relaxation associated with neighboring base pairs as well as the possibility of proton transfer along the N2(G)¡VH¡E¡E¡EO2(C) channel have also been investigated. The implications of the present findings to the electron transport and radiation damage of DNA are discussed.

La structure du noyau N = Z doublement magique 56Ni (N = 28, Z = 28) a été étudiée en mesurant les réactions de transfert á un et deux nucléons. Le transfert nous donne des informations sur deux aspects physiques différents: la fermeture de couche N=28 et l’intensité de l’appariement neutron-proton. Le nombre magique N=28 est particulier, car c’est le premier créé par le spin-orbit. La double magicité permet la détermination de la nature de particule indépendante des voisins N±1 par réaction de transfert d’un nucléon. De plus, en tant que noyau N=Z a couches fermeés, le 56Ni est un noyau clé pour l’étude de l’apparement np dans la plus grande couche accessible expérimentalement. L’apparement np se manifeste dans le canal isoscalaire (T=0) et isovecteur (T=1). L’intensité relative de chaque canal révèle la nature collective des états. L’expérience de ce travail a eu lieu au GANIL-Caen, en France, avec un faisceau radioactif de 56Ni á 30MeV / u produit par frag- mentation de 58Ni et purification avec le spectromètreLISE. Les mesures ont été effectuées en cinématique inverse sur des cibles CH2 et CD2. Les détecteurs MUST2 et TIARA ont été utilisés pour la détection de éjectiles légers et couvraient presque 4π. En outre, quatre détecteurs germanium d’EXOGAM ont été utilisés pour les coïncidences de particules-gamma afin d’identifier l’état peuplé du résidu de réaction. Pour étudier le gap de N=28, nous étudions la spectroscopie du 55Ni par les réactions de transfert de nucléons (d, t) et (p, d) sur le 56Ni. Le spectre en énergie d’excitation est déduit de la mesure des éjectiles légers seulement. Ensuite,les coincidences particule-gamma sont utilisées pour améliorer la résolution et identifier les principaux états peuplés. La comparaison des distributions angulaires ainsi obtenues avec des calculs DWBA permet d’extraire les facteurs spectroscopiques pour les états de particules et de trous ainsi peuplés. En ce qui concerne l’appariement np, nous avons analysé la réaction 56Ni(d,α)54Co qui réalise un transfert de paires neutron-proton. Un affaiblissement du canal T=0 á cause de l’effet du spin-orbite est attendu. La sélectivité en ∆T=0 de la réaction (d, α) permet d’étudier plus en détail le canal isoscalaire T = 0. / The structure of the unstable doubly ma- gic nucleus 56Ni has been investigated by measuring one- and two-nucleon transfer reactions. Each trans- fer reaction provides information for two different physical aspects: the robustness of the N=28 shell gap and the strength of the neutron-proton pairing. 56Ni is a self-conjugate doubly magic nucleus with N=28 and Z=28. The magic number 28 is a peculiar shell closure created by spin-orbit splitting effects. The double magicity makes the determination of the single-particle nature of their N±1 neighbors by one-neutron transfer reaction of major interest to test both the robustness of shell closures as well as the evolution of particle and/or valence orbitals. Moreover 56Ni, as a N=Z nucleus with fully closed shells, is a key nucleus to investigate neutron-proton pairing in the largest shell accessible experimentally, the fp shell. Neutron-proton pairing can occur both in the isoscalar (T=0) and in the isovector (T=1) channels. The relative intensity of both channels reveals the collective nature of the states. The radioactive beam of 56Ni was produced at GANIL-Caen, France at 30 MeV/u by fragmentation of 58Ni and purification with the LISE spectrometer. The experimental set-up used, consists of the TIARA- MUST2-EXOGAM combination which provides an al- most 4π coverage and the ability to perform particle- γ coincidences. To probe the N=28 gap, we studied the spectroscopy of 55Ni through one-nucleon trans- fer reactions on 56Ni. The excitation energy spectrum is deduced by measuring the light ejectiles only, while particle-γ coincidences are used to improve the re- solution of the populated states and select the main ones. Comparison in between the extracted angular distributions and DWBA calculations allow the extraction of the spectroscopic strength of the hole- and particle- states populated by these one neutron pick- up reactions. As for neutron-proton pairing, a weakening of the strength is expected in the T=0 channel from previous results. The selectivity in ∆T=0 of the 56Ni(d,α)54Co reaction enables further investigation of the isoscalar channel contribution.

La physique à la drip-line offre l'opportunité d'étudier les noyaux à la limite du paysage couvert par la physique nucléaire, où l'addition de nouveaux protons et neutrons ne peut plus être supportée. A l'approche de la drip-line, la structure même des noyaux se trouve modifiée par rapport aux plus stables. Les fermetures de couches classiques disparaissent et de nouveaux phénomènes surgissent, tels que la clusterisation et les halos. Dans ce travail, nous avons revisité la spectroscopie du noyau non-lié 10He par l'intermédiaire d'une réaction de transfert d'un proton 11Li(d,3He) à 50 AMeV étudiée par la méthode de masse manquante. Pour ce faire, nous avons utilisé le détecteur MUST2 sur la ligne RIPS du RIKEN Nishina center. La partie expérimentale de ce travail repose sur un dispositif novateur utilisant des détecteurs de silicium très fins. Pour la première fois, la mise en oeuvre de ces derniers en conjonction avec des détecteurs sensibles en position de haute granularité a été démontrée. L'approche par réaction de transfert conduit à des résultats très clairs sur la position du premier état résonant du 10He, trouvé dans ce travail à 1.4(3) MeV, en accord avec la plupart des précédents travaux expérimentaux. L'obtention pour la première fois d'un facteur spectroscopique permet de nous renseigner sur la nature du recouvrement <10He|11Li>, trouvé égale à 0.13(6).

Oxygenated volatile organic compounds ((O)VOCs) contribute to ozone formation, affect the oxidising capacity of the troposphere and are sources of growth, and in some cases formation, of aerosols. It is therefore important to identify and quantify sources of (O)VOCs in the troposphere. In the late 1990s a unique technique for quantification of organic trace gas species, proton transfer reaction mass spectrometry (PTR-MS) was developed. PTR-MS potentially offers rapid response and high sensitivity without the need for sample pre-concentration. Concentrations can be derived from the PTR-MS either by calibration or can be calculated from measured ion count rates and kinetic considerations. In this work, the methodology of PTR-MS application is critically assessed. The uncertainties and inaccuracies associated with each parameter employed in the calculation of concentrations are reviewed. This includes a critical appraisal of models for the calculation of the collisional rate constant currently applied in the field of PTR-MS. The use of a model to account for the effects of the electric field, available in the literature but not previously applied to the PTR-MS, is advocated. Collisional rate constants employing each of the models discussed have been calculated for the reactions of H3O+ with over 400 molecules for PTR-MS. In PTR-MS it cannot be assumed that the product ion occurs only at the protonated non-dissociated mass. Few product distributions obtained from PTR-MS are cited in the literature, and even then the reaction chamber conditions (pressure, temperature and electric field strength) are not always specified. A large volume of product distributions for trace gases with H3O+ in select ion flow tube mass spectrometry (SIFT) exists in the literature and is reviewed. In SIFT, no electric field is applied to the reaction chamber and the extent and even nature of fragmentation can differ in PTR-MS. In addition to the application of an electric field, the energy in the reaction chamber can be increased by increasing the temperature or by variation of the reagent ion. In this work, the increase in energy via the three methods is approximated to enable a comparison of product distributions. The review of product distributions in PTR-MS, select ion flow drift tube mass spectrometry (SIFDT), variable temperature select ion flow tube mass spectrometry (VT-SIFT), SIFT, proton transfer reaction time of flight mass spectrometry (PTR-TOF-MS), proton transfer reaction ion trap mass spectrometry (PTR-ITMS) and electron ionisation mass spectrometry (EI-MS) is used alongside thermodynamic considerations to collate a list of potential contributors to a range of mass to charge ratios (m/z) in the PTR-MS. The need for further measurements of product distributions as a function of temperature, pressure and electric field strength for a wider range of (O)VOCs is highlighted. This enables dissociation to be better used as a tool for compound identification rather than being considered a hindrance. The collation of likely product distributions is applied to identify possible contributors to m/z observed during PTR-MS measurements of emission from cattle slurry. Field measurements were made during fertilisation of a grassland site south of Edinburgh in 2004 and 2005 and in laboratory-based measurements in 2006. Contextual reasoning, previous measurements and isotope ratios are used to narrow the list of possible contributors. Large concentrations of m/z cautiously identified as alcohols followed by a latter peak in carboxylic acids were observed during laboratory measurements. Increases in the corresponding m/z were also observed during the fertilisations. Other tentatively identified compounds emitted included phenol, methyl phenol, trimethylamine, and various sulphur containing compounds.

Electrospray ionization mass spectrometry (ESIMS) is widely used to characterize neutral and ionic species in solvents. Typically, electrical, thermal, and pneumatic potentials are applied to create electrosprays from which charged ionic species are ejected for downstream analysis by mass spectrometry. Most recently, ESIMS has been exploited to investigate ambient proton transfer reactions at air-water interfaces in real time. We assessed the validity of these experiments via complementary laboratory experiments. Specifically, we characterized the products of two reaction scenarios via ESIMS and proton nuclear magnetic resonance (1H-NMR): (i) emulsions of pH-adjusted water and isoprene (C5H8) that were mechanically agitated, and (ii) electrosprays of pH-adjusted water that were collided with gas-phase isoprene. Our experiments unambiguously demonstrate that, while isoprene does not oligomerize in emulsions, it does undergo protonation and oligomerization in electrosprays, both with and without pH-adjusted water, confirming that C-C bonds form along myriad high-energy pathways during electrospray ionization. We also compared our experimental results with some quantum mechanics simulations of isoprene molecules interacting with hydronium at different hydration levels (gas versus liquid phase). In agreement with our experiments, the kinetic barriers to protonation and oligomerization of isoprene were inaccessible under ambient conditions. Rather, the gas-phase chemistries during electrospray ionization drove the oligomerization of isoprene. Therefore, we consider that ESIMS could induce artifacts in interfacial reactions. These findings warrant a reassessment of previous reports on tracking chemistries under ambient conditions at liquid-vapor interfaces via ESIMS. Further, we took some high-speed images of electrosprays where it was possible to observe the main characteristics of the phenomena, i.e. Taylor cone, charge separation, and Coulomb fission. Finally, we took the freedom to speculate on possible mechanisms that take place during electrospray ionization that affected our system and possibly may influence other common analytical techniques on ESIMS.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21783号 / 工博第4600号 / 新制||工||1717(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 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.