No / Three new C-bonded cyclotriphosphazenes, [N3P3(2-thienyl)6], 2, [N3P3(3-thienyl)6], 4, and [N3P3(3,3-bithienyl-2,2-ylene)3], 6, have been prepared by two new synthetic procedures and are the first examples of non-spiro and trispirocyclotriphosphazene derivatives composed of thiophene and 3,3-dithiophene substituents, respectively. Their 1H, 13C and 31P NMR parameters are given. The solid state structures of 2, 4 and 6 have been determined by X-ray crystallography.

Indirect nuclear spin-spin coupling constants in high resolution nuclear magnetic resonance (NMR) spectroscopy provide the most powerful method for determining conformations and structures of molecules in solution. The research described in this dissertation establishes the conformational and substituent dependencies of several new types of nuclear spin-spin coupling for use in structural studies. It was also of interest to determine the electronic factors which lead to the observed experimental trends. Geminal, vicinal, and four-bond carbon-carbon nuclear magnetic resonance coupling constants were studied experimentally with fifty carbon-13 enriched alicyclic compounds. Because of the small magnitudes of many of these coupling constants it ~vas necessary to modify existing Fourier transform NMR equipment to perform J-resolved two-dimensional NMR experiments. With the greater spectral resolution it was possible to determine 56 intercarbon geminal (²J(cc)), 107 vicinal (³J(cc)) and 26 four-bond (⁴J(cc)) coupling constants. These data represent the largest collection of ²J(cc), the only known data for ⁴J(cc), and the most accurate compilation of vicinal ¹³C-¹³C coupling constants. In combination with molecular orbital methods, the relevant conformational and substituent trends in each of these series were elucidated. Because of the great amount of interest in the importance of bridgehead interactions in "strained" molecules, a study is presented of coupling transmitted via nonbonded interactions between the bridgehead carbons in a series of l-substituted-bicycloalkanes. The two-dimensional Fourier transform methods were again used to obtain the experimental coupling constants and molecular orbital methods were used to determine the importance of the intercarbon bridgehead interactions on ¹H-¹H, ¹³c-¹H, ¹³C-¹³C, ¹³c-¹⁹F , and ¹H-¹⁹F coupling constants. In all cases the nonbonded interactions increased dramatically as the separation between the bridgehead carbons decreased. Further understanding of mechanisms of "through space" coupling were based on NMP. studies of the long range coupling constants (⁵J(HF) and ⁴J(HF)) in N-methyl-8-fluoroquinolinium halides. The X-ray structure of N-methyl-8-fluoroquinolinium chloride was determined in an attempt to calculate the observed ⁵J(HF) and ⁴J(HF). A selective population inversion mIR method was used to show that the sign of ⁵J(HF) in N-ethyl-8- fluoroquinolinium iodide is positive.

No description available.

No description available.

We present and explore a new formulation of perturbative QCD based not on the renormalised coupling but on the dimensional transmutation parameter of the theory and the property of asymptotic scaling. The approach yields a continued function, the iterated function being that involved in the solution of the two-loop β-function equation. In the so-called large-b limit the continued function reduces to a continued fraction and the successive approximants are diagonal Padé approximants. We investigate numerically the convergence of successive approximants using the leading-b approximation, motivated by renormalons, to model the all-orders result. We consider the Adler D-function of vacuum polarisation, the Polarised Bjorken and Gross-Llewellyn Smith sum rules, the (unpolarised) Bjorken sum rule, and the Minkowskian quantities R(_r) and the R-ratio of e(^+)e(^-) annihilation. In contrast to diagonal Fade approximants the truncated continued function method gives remarkably stable large-order approximants in cases where infra-red renormalon effects are important. We also use the new approach to determine the QCD fundamental parameters from the R(_r) and the R-ratio measurements, where we find Ā(^(3))(_MS)=516±48 MeV (which yields a(_s)(µ=m(_r))=0.360(^+0.021)(_=0.020)), and Ā(^(5))(_MS)=299(^+6)(_-7) MeV (which yields a(_s)(µ=m(_zo)=0.1218±0.0004), respectively. The evolution of the former value to the m(_zo) energy results in a(_s)(µ= m(_zo)) = 0.123 ± 0.002. These values are in line with other determinations available in the literature. We implement the Complete Renormalisation Group Improvement (CORGI) scheme throughout all the calculations. We report on how the mathematical concept of Stieltjes series can be used to assess the convergence of Padé approximants of perturbative series. We find that the combinations of UV renormalons which occur in perturbative QCD may or may not be Stieltjes series depending on the renormalisation scheme used.

Three different aspects of the sinh-Gordon model are explored in this thesis. We begin, in chapter one, with a summary of the model and the necessary background. Chapter two studies the model with two boundary conditions. Two approaches are presented to investigate the reflection factors off the boundaries and the energy of the theory. In chapter three, perturbation theory is developed to study the theory with one general boundary condition. A contribution to the quantum reflection factor is obtained and compared with the result obtained for the special boundary condition. Chapters four and five investigate the supersymmetric extension of the model in the presence of a single boundary. Firstly, the classical limits of the supersymmetric reflection matrices are checked. The exact reflection factors are studied perturbatively up to the second order of the coupling constant. Secondly, the perturbation theory and the path integral formalism are employed in the supersymmetric model to study the quantum reflection factors. We conclude with a brief sixth chapter describing the outlook for further investigations.

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2009. / Title from title screen (site viewed June 26, 2009). PDF text: x, 153 p. : ill. (some col.) ; 9 Mb. UMI publication number: AAT 3350442. Includes bibliographical references. Also available in microfilm and microfiche formats.

Orientador: Roberto Rittner Neto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T02:42:28Z (GMT). No. of bitstreams: 1 Silva_CaioRicardoFaiadda_M.pdf: 3324014 bytes, checksum: 2a09da96b3179c4cc07eb8d6923bcdd1 (MD5) Previous issue date: 2011 / Resumo: A introdução da dissertação consiste na breve descrição da racionalização de acoplamentos JCH (n = 1, 2 e 3), das etapas de cálculos teóricos e das duas técnicas recentemente implementadas no IQ-Unicamp: HSQC-TOCSY-IPAP e IPAP-HSQMBC. A primeira parte da seção Resultados e Discussão trata da determinação experimental dos acoplamentos nos derivados de adamantano. Na parte que aborda as constantes calculadas é mostrado que não há necessidade de alto rigor teórico nos cálculos de otimização de geometria para moléculas rígidas em estudos de constante de acoplamento. As estruturas otimizadas nos níveis de teoria PM3 e B3LYP não apresentaram diferenças nos parâmetros geométricos e nem nas constantes de acoplamento teóricas. Sendo assim, o tempo para a obtenção dos resultados utilizando o método PM3 é drasticamente diminuído. A última parte dos Resultados e Discussão consiste na racionalização os JCH. A introdução do substituinte no adamantano não provoca modificação estrutural e por isso as variações das JCH são atribuídas às interações hiperconjugativas. O aumento do JCßHß para todos os derivados e devido a interação do substituinte com o sCC ou sCC*. Já para os JCaHb e JCaHg é observado que para os substituintes CN, C(O)CH3 e C(O)NH2 a interacao sCaCb n*CO ou sCaCb n*CN, que retira densidade eletrônica do caminho do acoplamento, não permitem que haja aumento nessas constantes. Para os demais substituintes as interações NXs*CaCb, que aumenta a densidade eletrônica do caminho do acoplamento, são os responsaveis pelo aumento desse acoplamento / Abstract: In the Introduction section, there are short descriptions of the: a) rationalization of spin-spin couplings JCH (n = 1, 2 e 3); b) the steps of theoretical calculations; and c) two NMR experiments recently implemented at IQ-UNICAMP: HSQC-TOCSY-IPAP and IPAP-HSQMBC. The first part of Results and Discussion approaches the experimental determination of the spin-spin coupling constants (SSCC) in adamantane derivatives. The second part approaches theoretical spin-spin coupling constants. In this part is shown that isn ft necessary high precision in theoretical calculations of geometry optimization for studies of spin-spin coupling constants in rigid molecules. The optimizated structures at PM3 and B3LYP level of theory present no difference geometrical parameters as well as the theoretical values of SSCC. The results lead a decrease in the computational efforts. The last part of Results and Discussion is about rationalization of JCH. The substituent in adamantane doesn ft cause structural changes, so the variations in JCH are attributed to hyperconjugation. The increase in JCßHß for all derivatives is due to interaction between substituent and C-C bond (sCC or sCC*). For the JCaHb and JCaHg is observed that for the CN, C(O)CH3 and C(O)NH2 substituents the interaction sCaCb n*CO ou sCaCb n*CN, which removes electronic density in coupling pathway, doesn ft allow no increase in these constants. For the others substituents interactions NXs*CaCb, which increases electronic density in coupling pathway, are responsible for the increase in these spin-spin coupling constants / Mestrado / Quimica Organica / Mestre em Química

Orientador: Roberto Rittner Neto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T16:43:04Z (GMT). No. of bitstreams: 1 Martins_CarinaRabelo_M.pdf: 2440804 bytes, checksum: 5902fcc19589dcc81792e0806f7ae9f6 (MD5) Previous issue date: 2005 / Resumo: Este trabalho apresenta estudos sobre o isomerismo conformacional das 2-halociclopentanonas (halo= cloro e bromo) utilizando a constante de acoplamento JHH, cálculos teóricos e a teoria de solvatação. Foi realizada a otimização das geometrias e das energias dos confôrmeros mais estáveis na forma C2 (meia cadeira) dos diferentes compostos, utilizando o programa Gaussian 98, sendo que a conformação mais estável obtida no vácuo foi a pseudo-axial para todos os compostos estudados. Os dados experimentais de JHH dos derivados clorado e bromado, juntamente com o resultado da otimização das geometrias e das energias nos níveis B3LYP e MP2 foram tratados computacionalmente pelos programas Models e BESTFIT, o que permitiu a análise do equilíbrio conformacional destes compostos em diferentes solventes. Os dados obtidos apontam para uma estabilização do confôrmero pseudo-equatorial (de maior momento de dipolo) de acordo com o aumento da polaridade do solvente, conforme o esperado. Estes resultados foram comparados aos resultados obtidos pela análise dos espectros de infravermelho, cujos resultados também mostram a estabilização do confôrmero pseudo-equatorial com o aumento da polaridade do meio. / Abstract: The present work reports an NMR metthod using the variation of the JHH coupling constants with the solvents, togethr with theoretical calculations and solvation theory for the conformational analysis of 2-halocyclopentanones (halo = chlorine and bromine). The results trom Ab initio calculations, performed with GAUSSIAN 98 program using DFT/B3LYP and MP2, showed that the theories for the chlorine and bromine-derivatives. The pseudo-axial half-chair (C2) form is stable, in vapour phase, for both compounds. The H NMR spectra were obtained in solvents of various polarities. The essential parameters for the solvation energy calculations were obtained through MODELS program using the optimized geometries trom Gaussian. The best values of intrinsic coupling constants tor each conformer and the experimental energy difference, in the vapour, phase were obtained through BESTFIT program, using the experimental coupling constants and data from theoretical calculations. These gave that the pseudo-equatorial conformer is stabilized with the increase in the solvent polarity. The results were complemented with data from infrared spectroscopy, which are in complete agreement with theoretical data. / Mestrado / Quimica Organica / Mestre em Química

Lattice gauge theory is a special regularization of continuum gauge theories and the numerical simulation of lattice quantum chromodynamics (QCD) remains as the only first principle method to study non-perturbative QCD at low energy. The lattice spacing a, which serves as the ultraviolet cut off, plays a significant role in determining error on any lattice simulation results. Physical results come from extrapolating a series of simulations with different values for a to a=0. Reducing the size of these errors for non-zero a improves the extrapolation and minimizes the error. In the strong coupling limit the coarse lattice spacing pushes the analysis of the finite lattice spacing error to its limit. Section 4 measures two renormalized physical observables, the neutral kaon mixing parameter BK and the Delta I=3/2 K pi pi decay amplitude A2 on a lattice with coarse lattice spacing of a ~ 1GeV and explores the a^2 scaling properties at this scale. In the weak coupling limit the lattice simulations suffer from critical slowing down where for the Monte Carlo Markov evolution the cost of generating decorrelated samples increases significantly as the lattice spacing decreases, which makes reliable error analysis on the results expensive. Among the observables the topological charge of the configurations appears to have the longest integrated autocorrelation time. Based on a previous work where a diffusion model is proposed to describe the evolution of the topological charge, section 2 extends this model to lattices with dynamical fermions using a new numerical method that captures the behavior for different Fourier modes. Section 3 describes our effort to find a practical renormalization group transformation to transform lattice QCD between two different scales, whose knowledge could ultimately leads to a multi-scale evolution algorithm that solves the problem of critical slowing down. For a particular choice of action, we have found that doubling the lattice spacing of a fine lattice yields observables that agree at the few precent level with direct simulations on the coarser lattice. Section 5 aims at speeding up the lattice simulations in the weak coupling limit from the numerical method and hardware perspective. It proposes a preconditioner for solving the Dirac equation targeting the ensemble generation phase and details its implementation on currently the fastest supercomputer in the world.