969 resultados para FUNCTIONAL THEORY CALCULATIONS


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Experimentally and theoretically determined infrared spectra are reported for a series of straight-chain perfluorocarbons: C2F6, C3F8, C4F10, C5F12, C6F14, and C8F18. Theoretical spectra were determined using both density functional (DFT) and ab initio methods. Radiative efficiencies (REs) were determined using the method of Pinnock et al. (1995) and combined with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). Theoretically determined absorption cross sections were within 10% of experimentally determined values. Despite being much less computationally expensive, DFT calculations were generally found to perform better than ab initio methods. There is a strong wavenumber dependence of radiative forcing in the region of the fundamental C-F vibration, and small differences in wavelength between band positions determined by theory and experiment have a significant impact on the REs. We apply an empirical correction to the theoretical spectra and then test this correction on a number of branched chain and cyclic perfluoroalkanes. We then compute absorption cross sections, REs, and GWPs for an additional set of perfluoroalkenes.

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The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

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B3LYP/6-31++G** calculations to study seven tautomers of 5-methylcytosine in aqueous media have been carried out. Optimized geometries and relative stabilities for the different tautomers have been calculated in the gas phase, including interaction with two discrete water molecules and taking into account the solvent effects by using the self-consistent reaction field theory. The role of specific and bulk contributions of solvent effect on the observable properties of the 5-methylcytosine is clarified. The amino-oxo form is the most abundant tautomer in aqueous media. A reaction pathway connecting amino-oxo and amino-hydroxy forms along the corresponding transition structures has been characterized. Good agreement between theoretical and available experimental results of harmonic vibration frequencies is found. (C) 2001 Elsevier B.V. B.V. All rights reserved.

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This thesis is concerned with calculations in manifestly Lorentz-invariant baryon chiral perturbation theory beyond order D=4. We investigate two different methods. The first approach consists of the inclusion of additional particles besides pions and nucleons as explicit degrees of freedom. This results in the resummation of an infinite number of higher-order terms which contribute to higher-order low-energy constants in the standard formulation. In this thesis the nucleon axial, induced pseudoscalar, and pion-nucleon form factors are investigated. They are first calculated in the standard approach up to order D=4. Next, the inclusion of the axial-vector meson a_1(1260) is considered. We find three diagrams with an axial-vector meson which are relevant to the form factors. Due to the applied renormalization scheme, however, the contributions of the two loop diagrams vanish and only a tree diagram contributes explicitly. The appearing coupling constant is fitted to experimental data of the axial form factor. The inclusion of the axial-vector meson results in an improved description of the axial form factor for higher values of momentum transfer. The contributions to the induced pseudoscalar form factor, however, are negligible for the considered momentum transfer, and the axial-vector meson does not contribute to the pion-nucleon form factor. The second method consists in the explicit calculation of higher-order diagrams. This thesis describes the applied renormalization scheme and shows that all symmetries and the power counting are preserved. As an application we determine the nucleon mass up to order D=6 which includes the evaluation of two-loop diagrams. This is the first complete calculation in manifestly Lorentz-invariant baryon chiral perturbation theory at the two-loop level. The numerical contributions of the terms of order D=5 and D=6 are estimated, and we investigate their pion-mass dependence. Furthermore, the higher-order terms of the nucleon sigma term are determined with the help of the Feynman-Hellmann theorem.

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In this thesis we develop further the functional renormalization group (RG) approach to quantum field theory (QFT) based on the effective average action (EAA) and on the exact flow equation that it satisfies. The EAA is a generalization of the standard effective action that interpolates smoothly between the bare action for krightarrowinfty and the standard effective action rnfor krightarrow0. In this way, the problem of performing the functional integral is converted into the problem of integrating the exact flow of the EAA from the UV to the IR. The EAA formalism deals naturally with several different aspects of a QFT. One aspect is related to the discovery of non-Gaussian fixed points of the RG flow that can be used to construct continuum limits. In particular, the EAA framework is a useful setting to search for Asymptotically Safe theories, i.e. theories valid up to arbitrarily high energies. A second aspect in which the EAA reveals its usefulness are non-perturbative calculations. In fact, the exact flow that it satisfies is a valuable starting point for devising new approximation schemes. In the first part of this thesis we review and extend the formalism, in particular we derive the exact RG flow equation for the EAA and the related hierarchy of coupled flow equations for the proper-vertices. We show how standard perturbation theory emerges as a particular way to iteratively solve the flow equation, if the starting point is the bare action. Next, we explore both technical and conceptual issues by means of three different applications of the formalism, to QED, to general non-linear sigma models (NLsigmaM) and to matter fields on curved spacetimes. In the main part of this thesis we construct the EAA for non-abelian gauge theories and for quantum Einstein gravity (QEG), using the background field method to implement the coarse-graining procedure in a gauge invariant way. We propose a new truncation scheme where the EAA is expanded in powers of the curvature or field strength. Crucial to the practical use of this expansion is the development of new techniques to manage functional traces such as the algorithm proposed in this thesis. This allows to project the flow of all terms in the EAA which are analytic in the fields. As an application we show how the low energy effective action for quantum gravity emerges as the result of integrating the RG flow. In any treatment of theories with local symmetries that introduces a reference scale, the question of preserving gauge invariance along the flow emerges as predominant. In the EAA framework this problem is dealt with the use of the background field formalism. This comes at the cost of enlarging the theory space where the EAA lives to the space of functionals of both fluctuation and background fields. In this thesis, we study how the identities dictated by the symmetries are modified by the introduction of the cutoff and we study so called bimetric truncations of the EAA that contain both fluctuation and background couplings. In particular, we confirm the existence of a non-Gaussian fixed point for QEG, that is at the heart of the Asymptotic Safety scenario in quantum gravity; in the enlarged bimetric theory space where the running of the cosmological constant and of Newton's constant is influenced by fluctuation couplings.

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Performing three-dimensional pin-by-pin full core calculations based on an improved solution of the multi-group diffusion equation is an affordable option nowadays to compute accurate local safety parameters for light water reactors. Since a transport approximation is solved, appropriate correction factors, such as interface discontinuity factors, are required to nearly reproduce the fully heterogeneous transport solution. Calculating exact pin-by-pin discontinuity factors requires the knowledge of the heterogeneous neutron flux distribution, which depends on the boundary conditions of the pin-cell as well as the local variables along the nuclear reactor operation. As a consequence, it is impractical to compute them for each possible configuration; however, inaccurate correction factors are one major source of error in core analysis when using multi-group diffusion theory. An alternative to generate accurate pin-by-pin interface discontinuity factors is to build a functional-fitting that allows incorporating the environment dependence in the computed values. This paper suggests a methodology to consider the neighborhood effect based on the Analytic Coarse-Mesh Finite Difference method for the multi-group diffusion equation. It has been applied to both definitions of interface discontinuity factors, the one based on the Generalized Equivalence Theory and the one based on Black-Box Homogenization, and for different few energy groups structures. Conclusions are drawn over the optimal functional-fitting and demonstrative results are obtained with the multi-group pin-by-pin diffusion code COBAYA3 for representative PWR configurations.

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Different types of spin–spin coupling constants (SSCCs) for several representative small molecules are evaluated and analyzed using a combination of 10 exchange functionals with 12 correlation functionals. For comparison, calculations performed using MCSCF, SOPPA, other common DFT methods, and also experimental data are considered. A detailed study of the percentage of Hartree–Fock exchange energy in SSCCs and in its four contributions is carried out. From the above analysis, a combined functional formed with local Slater (34%), Hartree–Fock exchange (66%), and P86 correlation functional (S66P86) is proposed in this paper. The accuracy of the values obtained with this hybrid functional (mean absolute deviation of 4.5 Hz) is similar to that of the SOPPA method (mean absolute deviation of 4.6 Hz).

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Mathematics Subject Classification: 26A33, 34A60, 34K40, 93B05

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Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

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Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

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Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

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In this paper we study the existence of global solutions for a class of abstract functional differential equation with nonlocal conditions. An application is considered.

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We show that the one-loop effective action at finite temperature for a scalar field with quartic interaction has the same renormalized expression as at zero temperature if written in terms of a certain classical field phi(c), and if we trade free propagators at zero temperature for their finite-temperature counterparts. The result follows if we write the partition function as an integral over field eigenstates (boundary fields) of the density matrix element in the functional Schrodinger field representation, and perform a semiclassical expansion in two steps: first, we integrate around the saddle point for fixed boundary fields, which is the classical field phi(c), a functional of the boundary fields; then, we perform a saddle-point integration over the boundary fields, whose correlations characterize the thermal properties of the system. This procedure provides a dimensionally reduced effective theory for the thermal system. We calculate the two-point correlation as an example.

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We use the boundary effective theory approach to thermal field theory in order to calculate the pressure of a system of massless scalar fields with quartic interaction. The method naturally separates the infrared physics, and is essentially nonperturbative. To lowest order, the main ingredient is the solution of the free Euler-Lagrange equation with nontrivial (time) boundary conditions. We derive a resummed pressure, which is in good agreement with recent calculations found in the literature, following a very direct and compact procedure.