The success of many experiments at rare-isotope facilities, such as the National Superconducting Cyclotron Laboratory (NSCL), depends on achieving a level of statistics that is partly driven by the overall number of nuclei produced in the beam. One such future study at the NSCL requires maximizing the beam content of 34mCl. To prepare for this 34mCl study, an initial measurement to determine the 34mCl yields and overall beam purity was performed at the NSCL by utilizing a Beta-decay experimental station. Isotopes delivered to the experimental station were identified using standard time of flight and energy loss techniques. To explore ways of maximizing 34mCl production, 6 different beam energy settings that selected different rigidities for isotopic selection and altered its entrance angles before the beam went into the fragment separator, were utilized. The absolute intensity of the peak energies associated with the decay of 34mCl (1177, 2127, and 3304 keV) were determined, as well as the overall number of 34Cl atoms delivered, thereby enabling 34mCl yield and beam purity determinations for each beam setting.

No description available.

The structural properties of the very neutron deficient systems around N~Z~40 have been studied in two experiments performed at the GANIL and Legnaro laboratories. The fragmentation of a 60 MeV/u92 Mo beam on a natural nickel target at the GANIL Laboratory, France, produced exotic nuclei along the proton drip line in the mass 80 region. Isomeric decays have been observed for the first time in the N=Z+2 systems 74 36Kr, 80 39Y and 84 41Nb. The isomer in 74 Kr is interpreted as the hindered decay from an excited 0+ state, supporting the long-standing prediction of prolate/oblate shape coexistence in this nucleus. Transitions from states below an isomer in the N=Z nucleus 86 43Tc have also been tentatively identified, making this the heaviest N=Z system for which gamma-ray decays from excited states have been observed. Conclusive evidence for the existence of the Z=N+1 isotopes 77 39Y, 79 40Zr and 83 42Mo has also been obtained together with upper limits on the particle decay lifetimes of the odd-proton systems 81 41 Nb and 85 43Tc. The reported instability of the lighter odd-Z, Tz = -1/2 systems 69Br and 73Rb makes the observed existence for 77 39Y particularly interesting. A possible explanation for the relative particle stability of 77 39Y is given in terms of the shape polarising effect of the N=Z=38 prolate shell gap on the nuclear mean field and the increased centrifugal barrier associated with the occupation of a g9/2 proton orbital. The second experiment was performed to further investigate the oblate nature of the isomeric state in 74Kr. The reaction 40Ca(40Ca, alpha2p)74Kr was used at a beam energy of 135 MeV obtained from the Tandem XTU accelerator. The EUROBALL gamma-ray array was used in conjunction with the ISIS charged particle silicon ball to study the states above and below the isomer. The ISIS ball was used to highlight channel selection of non-yrast states by particle gating. No evidence for the 0+2 isomer in 74Kr was observed in this work.

This thesis contains investigations in two different areas, described under six chapters. Chapter 1 contains a broad introduction to the area of foldamers, while Chapters 2, 3, 4, and 5 deal with various novel classes of synthetic polymers which can form folded structures in solution utilizing different non-covalent interactions. Chapter 6 deals with a distinctly different topic, where the objective was to study the effect of phenyl ring location on the micellization properties of a series of isomeric cationic surfactants. Synthetic polymers typically adopt a random coil conformation in solution, which is primarily an entropy driven process. So the generation of well-defined secondary structures in synthetic polymers requires specific intra-chain inter-segment interactions that will give adequate enthalpic contribution to overcome the entropic penalty associated with the formation of well-ordered conformations. During the past decade, various research groups have made significant effort to understand the essential design elements that could enable secondary structure formation in synthetic macromolecules through intra-chain inter-segment interactions, such as hydrogen bonding, solvophobic and solvophilic interaction, acid-base interaction, bond angle constraint, steric interaction, charge-transfer interaction, metal-ion complexation etc.1 Gellman2 first used the term “foldamer” to describe “any polymer with a strong tendency to adopt a specific compact conformation” which was more precisely defined by Moore and coworkers3 as “any oligomer that folds into a conformationally ordered state in solution, the structures of which are stabilized by a collection of non-covalent interactions between nonadjacent monomer units” and where the folded conformation is one of the various possible conformations. Several classes of foldamers have been studied during the past decade; a majority of them are well-defined oligomers that possess relatively restricted conformational degrees of freedom. Relatively fewer studies have explored conformational control in flexible high molecular weight polymers that possess greater conformational freedom.4 A few years ago, Ghosh et al. designed a polymeric system wherein charge-transfer interactions between alternatively placed electron-rich and electron-deficient aromatic units, aided by metal-ion complexation and solvophobic interactions, causes the polymer chain to adopt a specific folded conformation.5 Such charge-transfer induced folding was first studied by Iverson and co-workers6 in well-defined oligomers and was later elaborated by Zhao et al.7 to generate alternate designs to fold oligomeric systems. In all these studies, the C-T interactions served not only to assist the folding process but it also served as a valuable spectroscopic signature to study the folding process. The objectives of the present study are to develop simple synthetic strategies to generate different types of polymers that could be fold in solution using various noncovalent interactions. We have developed a simple synthetic strategy to design a new type of donor (1,5-dialkoxynaphthalene-DAN) containing polymer that carries a tertiary amine unit in the spacer segment, which could interact strongly with a suitably designed acceptor (pyromellitic diimide-PDI) bearing folding agent that carries a carboxylic acid group, as shown in Scheme 1.8 This acid-base interaction, brings the acceptor unit in a suitable position so as to form a C-T complex with the adjacent donors, resulting in the folding of the polymer chain. The folded conformation was studied using UV-vis and NMR spectroscopy and the folding propensities were rationalized using DFT studies. The highest association constant between the folding agent and the polymer was estimated to be around 1200 M-1. Scheme 1. Schematic representation of folding aided by two-point interactions with a folding agent. This value of association constant was not adequate to realize some potentially interesting properties in solid state. In an attempt to develop alternate systems, that could exhibit stronger propensity to fold, we designed a new type of cationic ionene,9 wherein electron-rich (DAN) and electron-deficient (PDI) aromatic units were included within the alkylene segments in an alternating fashion, as shown in Scheme 2.10 The charge-transfer (C-T) interaction between the donor and acceptor units in neighbouring segments of the ionene not only reinforced the transition to the collapsed nano-bundle form but also provides a useful spectroscopic handle to monitor the conformational change. The UV-visible spectra of these novel D-A ionene solutions at a fixed concentration in four different solvents, namely water, methanol, acetonitrile and DMSO, show different extents of charge-transfer interaction. The colour of the solution in water was deep-red, whereas in acetonitrile, it was light-yellow. The conformational transition could also be induced by titrating an acetonitrile solution of the ionene with increasing amounts of water causing a dramatic increase in the intensity of the charge-transfer band, which reflects the extent of collapse to the zig-zag state that brings the donor and acceptor units together. AFM studies confirmed the presence of flat pancake-like aggregates having nearly constant height of about 3-5 nm, which was in accordance with the estimated thickness of the postulated zig-zag structure. Scheme 2. Schematic depiction of folding of D-A ionene (left), AFM micrograph showing pancake-like aggregates of D-A ionenes (right-top), a line scan depicting the heights and diameters of the aggregates along with a schematic depiction of the aggregate (right-bottom). Scheme 3. Schematic representation of folding aided by interactions with a folding agent. In order to explore this concept further, we designed a two component system wherein the solvophobically-driven collapse of a DAN-containing ionene chain in a polar solvent is reinforced by intercalation with a suitably designed electron-deficient acceptor-containing external folding agent. DAN containing ionene polymer chains in polar solvent form an accordion-type zig-zag structure that brings adjacent donor units in close proximity; this provided an ideal hydrophobic pocket for intercalation of suitably designed electron-deficient acceptor molecules, the additional driving motivation for the intercalation being the formation of a C-T complex as shown in Scheme 3.11 Several acceptor-bearing molecules were prepared by the derivatization of pyromellitic dianhydride and naphthalene tetracarboxylic dianhydride with two different oligoethylene glycol monomethyl ether monoamines. UV-vis spectroscopic studies were carried out by using a 1:1 mixture of the DAN-ionenes and different acceptor molecules in water/DMSO solvent mixtures. The intensity of the charge-transfer (C-T) band was seen to increase with the water content in the solvent mixture, thereby suggesting that the intercalation is indeed aided by solvophobic effects. The naphthalene diimide (NDI) bearing acceptor molecules consistently formed significantly stronger C-T complexes when compared to the pyromellitic diimide (PDI) bearing acceptor molecules, which is a reflection of the stronger π-stacking tendency of the former. The highest association constant between the folding agent and the polymer was estimated to be around 4519 M-1, which was a substantial improvement over the earlier reported values.9 With a slight modification in the pendant group, we designed a water-soluble DAN-containing ionene, which can intercalate hydrophobic electron-deficient molecules, like TNT (2,4,6-trinitrotoluene), within the hydrophobic interstices between DAN units (as shown in Scheme 4), causing a depletion in fluorescence from the DAN units; TNT at concentration as low as 30 nM could be detected in this manner. Scheme 4. Schematic representation of folding of water soluble ionene and interactions with an electron-deficient hydrophobic moiety TNT. Scheme 5. Schematic representation of folded D-A allyl ionene. In light of the growing interest in single-chain polymeric nanoparticles, the fully collapsed D-A ionenes in water could be viewed as polymeric nanoparticles that are stitched together by reversible weak noncovalent interactions. In an attempt to transform the folded structure into a polymeric nanoparticle using covalent bonding, we designed D-A ionene that carries potentially polymerizable allyl units on the cationic head group instead of the dimethyl amine head group that was used in previous examples (as shown in Scheme 5). Preliminary studies showed that polymerization does not proceed readily; however, thiol-ene based clicking strategy enabled partial stitching of the folded segments, by the use of a suitably designed dithiol. In the last section of this thesis, we examined the effect of phenyl ring location on the micellization properties of a series of isomeric cationic surfactants, wherein the phenyl ring location was varied from head to tail region (as shown in Scheme 6).12 Thus, cationic surfactants (S1-S5) bearing a long alkyl chain that carries a 1,4phenylene unit and a trimethyl ammonium headgroup was synthesized and their solution properties were examined. Micellization behavior was studied using conductivity, ITC (Isothermal Titration Calorimetry), SANS (Small-Angle Neutron Scattering) and NMR. These present studies demonstrated that the presence of a large rigid ring near the hydrocarbon tail-end of the surfactant leads to a dramatic change in the micelle structure; the driving motivation to form micelles in such systems is greatly reduced and the micelles that are formed are relatively smaller and contain significantly fewer surfactants. NMR studies of micellar solutions of these surfactants indicate that the variation in the phenyl ring location may also help to probe the microenvironment at various depths within the micellar aggregates. Scheme 6. Structures of the various surfactant molecules carrying the 1,4-dioxyphenylene unit at different locations within hydrophobic segment (left), variation of CMC values (right). References (1) Foldamers - structure, properties, and applications, edited by Stefan Hecht and Ivan Huc, Wiley-VCH, 2007. (2) Gellman, S. H. Acc. Chem. Res. 1998, 31, 173. (3) Hill, D. J.; Mio, M. J.; Prince, R. B.; Huges, T. S.; Moore, J. S. Chem. Rev. 2001, 101, 3893. (4) (a) Wang, W.; Li, L. S.; Helms, G.; Zhou, H. H.; Li, A. D. Q. J. Am. Chem. Soc. 2003, 125, 1120. (b) Li, A. D. Q.; Wang, W.; Wang, L. Q. Chem. Eur. J. 2003, 9, 4594. (c) Neuteboom, E. E.; Meskers, S. C. J.; Meijer, E. W.; Janssen, R. A. J. Macromol. Chem. Phys. 2004, 205, 217. (d) Balbo Block, M. A.; Hecht, S. Macromolecules 2004, 37, 4761. (5) (a) Ghosh, S.; Ramakrishnan, S. Angew. Chem. Int. Ed. 2004, 43, 3264. (b) Ghosh, S.; Ramakrishnan, S. Angew. Chem. Int. Ed. 2005, 44, 5441. (6) Lokey, R. S.; Iverson, B. L. Nature 1995, 375, 303. (7) Zhao, X.; Jia, M. X. Jiang, X. K.; Wu, L. Z.; Li, Z. T.; Chen. G. J. J. Org. Chem. 2004, 69, 270. (8) De, S.; Koley, D.; Ramakrishnan, S. Macromolecules 2010, 43, 3183. (9) Williams, S. R.; Long, T. E. Prog. Polym. Sci. 2009, 34, 762. (10) De, S.; Ramakrishnan, S. Macromolecules 2009, 42, 8599. (11) De, S.; Ramakrishnan, S. Chem. Asian J. 2011, 6, 149. (12) De, S.; Aswal, V. K.; Ramakrishnan, S. Langmuir 2010, 26, 17882. (For structural formula pl see the abstract file.

The general fission process is well known and is applied in nuclear power plants all over the world. However many properties of fission fragments are still not well understood. The angular momentum distribution of fission fragments is an important property to gain a better understanding of the fission process, and that can be derived indirectly from isomeric yield ratios. The goal of this project has been to develop a script in Python that runs the nuclear reaction code TALYS with the Total Monte Carlo method to calculate the isomeric yield ratio. The script generates a matrix consisting of excitation energies and angular momenta that is provided to TALYS. One matrix corresponds to one calculation of the isomeric ratio. Thus, the dependency of the isomeric yield ratio on these matrices can be observed. After looking into the matrices, the dependencies of the isomeric yield ratios on the excitation energies and the angular momentum distribution are observed. In this project, the calculated isomeric yield ratios are compared with the experimental value obtained from an experiment conducted in August of 2019 at the IGISOL-JYFLTRAP facility in Jyväskylä, Finland. It is worth mentioning that, fission system is of Uranium-238 which was induced by a proton beam at an energy of 25 MeV. The dependency of the isomeric yield ratio (IYR) on the angular momentum and the excitation energy has been investigated. However, it has proved more difficult than expected, to deduce an estimation for the angular momentum distribution. Another finding of this project is that the two codes used, GEF and TALYS sometimes produce inconstant results.

No description available.

La fission nucléaire consiste en la brisure d'un noyau lourd, généralement un actinide, en deux noyaux plus légers (ou trois dans quelques rares cas). Ce phénomène a été découvert par Hahn et Strassman en 1938. Très rapidement Meitner et Frisch proposèrent une explication théorique pour ce processus à l'aide du modèle de la goutte liquide. Depuis les modèles n'ont cessé d'évoluer et de se complexifier à travers l'ajout de nouveaux mécanismes et l'observation de nouveaux phénomènes. L'amélioration des modèles est un enjeu important à la fois pour la compréhension fondamentale du processus de fission mais aussi pour les applications. En effet, le dimensionnement des réacteurs futurs s'appuie de plus en plus sur des simulations numériques. Il devient dès lors primordial de réduire les incertitudes associées aux données utilisées. Cela passe alors par la validation des hypothèses sous-jacentes des modèles de fission nucléaire.Dans le cadre de cette thèse, on s'intéresse à deux aspects de la fission nucléaire qui permettront de tester la robustesse des théories. L'un des aspects concerne l'étude des fragments de fission issus de la région de la symétrie à travers la mesure des rendements et des distributions en énergie cinétique. L'autre aspect étudié est le moment angulaire des fragments de fission.Afin d'accéder au moment angulaire des fragments de fission, l'une des possibilités est d'analyser les propriétés des particules promptes, qui est l'une des ambitions du projet FIPPS (FIssion Product Prompt gamma-ray Spectrometer). Une partie de ce travail a été de caractériser les propriétés des spectromètres magnétiques gazeux à travers des mesures expérimentales et le développement d'une simulation Monte Carlo.La seconde partie de ce travail a consisté en la mesure de rapports isomériques et en l'extraction de la distribution du moment angulaire des fragments de fission à l'aide d'un code de désexcitaiton nucléaire. La mesure d'un noyau doublement magique ($^{132}$Sn) permet de mettre en lumière les limites actuelles des modèles de fission.Enfin la dernière partie de ce travail porte sur la mesure des rendements et des distributions en énergie cinétique des fragments de fission. Certains modèles prédisent l'existence de modes dans la fission nucléaire. La région des masses symétriques est dès lors un lieu de choix pour vérifier la validité de ces affirmations.Il est à noter qu'en parallèle de ces études, un accent fort a été mis sur le développement de méthodes d'analyse s'appuyant sur des outils statistiques afin notamment d'améliorer l'évaluation des incertitudes expérimentales. / Nuclear fission consists in splitting a nucleus, in general an actinide, into smaller nuclei. Despite nuclear fission was discovered in 1939 by Hahn and Strassman, fission models cannot predict the fission observables with an acceptable accuracy for nuclear fuel cycle studies for instance. Improvement of fission models is an important issue for the knowledge of the process itself and for the applications. To reduce uncertainties of the nuclear data used in a nuclear reactor simulation, a validation of the models hypothesis is mandatory.In this work, two features of the nuclear fission were investigated in order to test the resistance of the theories. One aspect is the study of the symmetric fission fragments through the measurement of their yield and kinetic energy distribution. The other aspect is the study of the fission fragment angular momentum.Two techniques are available to assess the angular momentum of a fission fragment. The first one is to look at the properties of the prompt $gamma$. The new spectrometer FIPPS (FIssion Product Prompt gamma-ray Spectrometer), is currently under development at the ILL and will combine a fission filter with a large array of $gamma$ and neutron detectors in order to respond to these issues. The first part of this work is dedicated to the study of the properties of a Gas Filled Magnet (GFM) which is the type of fission filter considered for the FIPPS project.The second part of this work deals with the measurement of isomeric yields and evaluations of the angular momentum distribution of fission fragments. The study of the spherical nucleus $^{132}$Sn shed the light on the current limits of fission models.Finally, the last part of this work is about the measurement of the yields and kinetic energy distributions of symmetric fission fragments. Since models predict the existence of fission modes, the symmetry region is a suitable choice to investigate this kind of prediction.In parallel with all these studies, an emphasis on the development of new methods derived from statistical tools is achieved in order to better control the uncertainties and estimate the biases.

The Flory ideality hypothesis states that flexible polymer chains in a melt assume the shape of three-dimensional random walks leading to so called Gaussian coils. The basis of this hypothesis is that any local conformational information decays exponentially along the chain backbone and thus has no influence on the long range conformation. Additionally it is argued that the excluded volume shielding of neigbor chains cancels out any swelling effects. Neutron scattering (NS) experiments dating back 30 years confirm the postulated Gaussian coil shape of polymers. This leads to a pillar of polymer theory: Any flexible polymer can be described as a three-dimensional random walk. Advances in simulation technics and computing power have opened the door to the possibility of studing very long chains. This allowed for a closer look at the chain structure of polymer melts and revealed deviations from ideality. This deviation is very slight and thus great care must be taken to distinguish it from noise. So far the deviation from the Gaussian coil structure was only studied for coarse-grained models. The scope of this thesis is to explore if these deviations are also measurable in atomistically realistic simulations and modern day NS experiments.

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Selon l’hypothèse d’idéalité de Flory, les chaînes de polymères flexibles à l’état fondu se présentent sous la forme de marches aléatoires à trois dimensions, aussi appelées pelotes gaussiennes. Cette hypothèse suppose que toute information relative à la conformation locale subit une décroissance exponentielle le long de la chaîne principale et, par conséquent, n’a aucune influence sur la conformation à grande échelle. De plus, il est avancé que l’écrantage du volume exclu par les chaînes voisines compense tout effet de gonflement. Des expériences de diffusion neutronique (DN) effectuées il y a une trentaine d’années confirment que les polymères adoptent bien des configurations gaussiennes. S’ensuit l’un des piliers de la théorie des polymères : En solution ”suffisamment dense” tout polymère flexible peut être décrit comme une marche aléatoire à trois dimensions, indépendamment de sa structure chimique, et ce, après un rééchelonnage adéquat. Les progrès réalisés dans les domaines des techniques de simulation et de la puissance informatique ont rendu possible l’étude de chaînes très longues. Ceci a permis d’observer de plus près la structure des chaînes de polymère à l’état fondu et révélé une déviation par rapport à la chaîne idéale. Jusqu’à présent, la déviation par rapport à la structure gaussienne a uniquement été étudiée dans le cas de modèles à gros grains, par simulation et calcul analytique. La présente thèse cherche à vérifier si ces déviations peuvent également être mesurées à l’aide de simulations atomistiques réalistes et d’expériences de DN modernes. / The Flory ideality hypothesis states that flexible polymer chains in a melt assume the shape of three-dimensional random walks leading to so called Gaussian coils. The basis of this hypothesis is that any local conformational information decays exponentially along the chain backbone and thus has no influence on the long range conformation. Additionally it is argued that the excluded volume shielding of neigbor chains cancels out any swelling effects. Neutron scattering (NS) experiments dating back 30 years confirm the postulated Gaussian coil shape of polymers. This leads to a pillar of polymer theory: Any flexible polymer can be described as a three-dimensional random walk. Advances in simulation technics and computing power have opened the door to the possibility of studing very long chains. This allowed for a closer look at the chain structure of polymer melts and revealed deviations from ideality. This deviation is very slight and thus great care must be taken to distinguish it from noise. So far the deviation from the Gaussian coil structure was only studied for coarse-grained models. The scope of this thesis is to explore if these deviations are also measurable in atomistically realistic simulations and modern day NS experiments.