An anharmonic contribution to the Helmholtz free energy O(lambda 6)

The anharmonic contributions of order A6 to the Helmholtz free energy for a crystal in which every atom is on a site of inversion symmetry, have been evaluated The cor~esponding diagrams in the various orders of the perturbation theory have been presented The validity of the expressions given is for high temperatures. Numerical calculations for the diagrams which contribute to the free energy have been worked out for a nearest-n~ighbour central-force model of a facecentered cubic lattice in the high-temperature limit and in the leading term and the Ludwig approximations. The accuracy of the Ludwig approximation in evaluating the Brillouin-zone sums has been investigated. Expansion for all diagrams in the high-temperature limit has been carried out The contribution to the specific heat involves a linear as well as cubic term~ We have applied Lennard-Jones, Morse and Exponential 6 types of potentials. A comparison between the contribution to the free energy of order A6 to that of order A4 has been made.

Phonon spectra and temperature variation of thermodynamic properties of fcc metals via Finnis-Sinclair type many body potentials: Sutton-Chen and improved Sutton-Chen models

Volume(density)-independent pair-potentials cannot describe metallic cohesion adequately as the presence of the free electron gas renders the total energy strongly dependent on the electron density. The embedded atom method (EAM) addresses this issue by replacing part of the total energy with an explicitly density-dependent term called the embedding function. Finnis and Sinclair proposed a model where the embedding function is taken to be proportional to the square root of the electron density. Models of this type are known as Finnis-Sinclair many body potentials. In this work we study a particular parametrization of the Finnis-Sinclair type potential, called the "Sutton-Chen" model, and a later version, called the "Quantum Sutton-Chen" model, to study the phonon spectra and the temperature variation thermodynamic properties of fcc metals. Both models give poor results for thermal expansion, which can be traced to rapid softening of transverse phonon frequencies with increasing lattice parameter. We identify the power law decay of the electron density with distance assumed by the model as the main cause of this behaviour and show that an exponentially decaying form of charge density improves the results significantly. Results for Sutton-Chen and our improved version of Sutton-Chen models are compared for four fcc metals: Cu, Ag, Au and Pt. The calculated properties are the phonon spectra, thermal expansion coefficient, isobaric heat capacity, adiabatic and isothermal bulk moduli, atomic root-mean-square displacement and Gr\"{u}neisen parameter. For the sake of comparison we have also considered two other models where the distance-dependence of the charge density is an exponential multiplied by polynomials. None of these models exhibits the instability against thermal expansion (premature melting) as shown by the Sutton-Chen model. We also present results obtained via pure pair potential models, in order to identify advantages and disadvantages of methods used to obtain the parameters of these potentials.

Statistical potentials for evolutionary studies

Les séquences protéiques naturelles sont le résultat net de l’interaction entre les mécanismes de mutation, de sélection naturelle et de dérive stochastique au cours des temps évolutifs. Les modèles probabilistes d’évolution moléculaire qui tiennent compte de ces différents facteurs ont été substantiellement améliorés au cours des dernières années. En particulier, ont été proposés des modèles incorporant explicitement la structure des protéines et les interdépendances entre sites, ainsi que les outils statistiques pour évaluer la performance de ces modèles. Toutefois, en dépit des avancées significatives dans cette direction, seules des représentations très simplifiées de la structure protéique ont été utilisées jusqu’à présent. Dans ce contexte, le sujet général de cette thèse est la modélisation de la structure tridimensionnelle des protéines, en tenant compte des limitations pratiques imposées par l’utilisation de méthodes phylogénétiques très gourmandes en temps de calcul. Dans un premier temps, une méthode statistique générale est présentée, visant à optimiser les paramètres d’un potentiel statistique (qui est une pseudo-énergie mesurant la compatibilité séquence-structure). La forme fonctionnelle du potentiel est par la suite raffinée, en augmentant le niveau de détails dans la description structurale sans alourdir les coûts computationnels. Plusieurs éléments structuraux sont explorés : interactions entre pairs de résidus, accessibilité au solvant, conformation de la chaîne principale et flexibilité. Les potentiels sont ensuite inclus dans un modèle d’évolution et leur performance est évaluée en termes d’ajustement statistique à des données réelles, et contrastée avec des modèles d’évolution standards. Finalement, le nouveau modèle structurellement contraint ainsi obtenu est utilisé pour mieux comprendre les relations entre niveau d’expression des gènes et sélection et conservation de leur séquence protéique.

Studies on gaussian effective potentials in some models

In classical field theory, the ordinary potential V is an energy density for that state in which the field assumes the value ¢. In quantum field theory, the effective potential is the expectation value of the energy density for which the expectation value of the field is ¢o. As a result, if V has several local minima, it is only the absolute minimum that corresponds to the true ground state of the theory. Perturbation theory remains to this day the main analytical tool in the study of Quantum Field Theory. However, since perturbation theory is unable to uncover the whole rich structure of Quantum Field Theory, it is desirable to have some method which, on one hand, must go beyond both perturbation theory and classical approximation in the points where these fail, and at that time, be sufficiently simple that analytical calculations could be performed in its framework During the last decade a nonperturbative variational method called Gaussian effective potential, has been discussed widely together with several applications. This concept was described as a means of formalizing our intuitive understanding of zero-point fluctuation effects in quantum mechanics in a way that carries over directly to field theory.

Correlations derived from modern nucleon-nucleon potentials

Various modern nucleon-nucleon (NN) potentials yield a very accurate fit to the nucleon-nucleon scattering phase shifts. The differences between these interactions in describing properties of nuclear matter are investigated. Various contributions to the total energy are evaluated employing the Hellmann-Feynman theorem. Special attention is paid to the two-nucleon correlation functions derived from these interactions. Differences in the predictions of the various interactions can be traced back to the inclusion of nonlocal terms.

Hypernuclear structure with the new Nijmegen potentials

Information on level density for nuclei with mass numbers A?20250 is deduced from discrete low-lying levels and neutron resonance data. The odd-mass nuclei exhibit in general 47 times the level density found for their neighboring even-even nuclei at the same excitation energy. This excess corresponds to an entropy of ?1.7kB for the odd particle. The value is approximately constant for all midshell nuclei and for all ground state spins. For these nuclei it is argued that the entropy scales with the number of particles not coupled in Cooper pairs. A simple model based on the canonical ensemble theory accounts qualitatively for the observed properties.

Ionization potentials and radii of atoms and ions of element 105 (unnilpentium) and ions of tantalum derived from multiconfiguration Dirac-Fock calculations

Multiconfiguration relativistic Dirac-Fock (MCDF) values were calculated for the first five ionization potentials of element 105 (unnilpentium) and of the other group 5b elements (V, Nb, and Ta). Some of these ionization potentials in electron volts (eV) with uncertainties are: 105(0), 7.4±0.4; 105(1 +), 16.3 ±0.2; 105(2 +), 24.3 ± 0.2; 105(3 + ), 34.9 ± 0.5; and 105(4 + ), 44.9 ± 0.1. Ionization potentials for Ta(1+), Ta(2 +), and Ta(3 + ) were also calculated. Accurate experimental values for these ionization potentials are not available. Ionic radii are presented for the 2+, 3+, 4 +, and 5+ ions of element 105 and for the + 2 ions of vanadium and niobium. These radii for vanadium and niobium are not available elsewhere. The ionization potentials and ionic radii obtained are used to determine some standard electrode potentials for element 105. Born-Haber cycles and a form of the Born equation for the Gibbs free energy of hydration of ions were used to calculate the standard electrode potentials.

Analytical potentials for triatomic molecules from spectroscopic data V. Application to HOX (X=F, Cl, Br, I)

Analytical potential energy functions are reported for HOX (X=F, Cl, Br, I). The surface for HOF predicts two metastable minima as well as the equilibrium configuration. These correspond to HFO (bent) and OHF (linear). Ab initio calculations performed for the HOF surface confirm these predictions. Comparisons are drawn between the two sets of results, and a vibrational analysis is undertaken for the hydrogen bonded OHF species. For HOCl, one further minimum is predicted, corresponding to HClO (bent), the parameters for which compare favourably with those reported from ab initio studies. In contrast, only the equilibrium configurations are predicted to be stable for HOBr and HOI.

Analytical potentials for triatomic molecules VIII. A two valued surface for the lowest 1A¢ surfaces of H2O

Ab initio calculations of the energy have been made at approximately 150 points on the two lowest singlet A' potential energy surfaces of the water molecule, 1A' and 1A', covering structures having D∞h, C∞v, C2v and Cs symmetries. The object was to obtain an ab initio surface of uniform accuracy over the whole three-dimensional coordinate space. Molecular orbitals were constructed from a double zeta plus Rydberg basis, and correlation was introduced by single and double excitations from multiconfiguration states which gave the correct dissociation behaviour. A two-valued analytical potential function has been constructed to fit these ab initio energy calculations. The adiabatic energies are given in our analytical function as the eigenvalues of a 2 2 matrix, whose diagonal elements define two diabatic surfaces. The off-diagonal element goes to zero for those configurations corresponding to surface intersections, so that our adiabatic surface exhibits the correct Σ/II conical intersections for linear configurations, and singlet/triplet intersections of the O + H2 dissociation fragments. The agreement between our analytical surface and experiment has been improved by using empirical diatomic potential curves in place of those derived from ab initio calculations.

A variational method for the calculation of spin-rovibronic energy levels of any triatomic molecule in an electronic triplet state

The triatomic spin-rovibronic variational code RVIB3 has been extended to include the effect of two uncoupled electrons, for both (3)Sigma(-) and (3)Pi (Renner-Teller) electronic states. The spin-orbital-rotational kinetic energy is included in the usual way, via terms (J+L+S). The phenomenological terms AL.S and lambda 2/3(3S(z)(2)) are introduced to reproduce the 3 spin-orbit and spin-spin splittings, respectively. Calculations are performed to evaluate the spin-rovibronic energy levels of CCO (X) over tilde (3) Sigma(-) and CCO (A) over tilde (3) Pi for which the Born-Oppenheimer potentials are derived from high-accuracy ab initio calculations.

Vibrational energy levels for the electronic ground state of the diazocarbene (CNN) molecule

The vibrational energy levels of diazocarbene (diazomethylene) in its electronic ground state, (X) over tilde (3) Sigma(-) CNN, have been predicted using the variational method. The potential energy surfaces of (X) over tilde (3) A" CNN were determined by employing ab initio single reference coupled cluster with single and double excitations (CCSD), CCSD with perturbative triple excitations [CCSD(T)], multi-reference complete active space self-consistent-field (CASSCF), and internally contracted multi-reference configuration interaction (ICMRCI) methods. The correlation-consistent polarised valence quadruple zeta (cc-pVQZ) basis set was used. Four sets of vibrational energy levels determined from the four distinct analytical potential functions have been compared with the experimental values from the laser-induced fluorescence measurements of Wurfel et al. obtained in 1992. The CCSD, CCSD(T), and CASSCF potentials have not provided satisfactory agreement with the experimental observations. In this light, the importance of both non-dynamic (static) and dynamic correlation effects in describing the ground state of CNN is emphasised. Our best theoretical fundamental frequencies at the cc-pVQZ ICMRCI level of theory, v(1) = 1230, v(2) = 394, and v(3) = 1420 cm(-1) are in excellent agreement with the experimental values of v(1) = 1235, v(2) = 396, and v(3) = 1419cm(-1) and the mean absolute deviation between the 23 calculated and experimental vibrational energy levels is only 7.4 cm(-1). It is shown that the previously suggested observation of the v(3) frequency at about 2847cm(-1) was in fact the first overtone 2v(3).

A FORTRAN-90 low-energy electron diffraction program (LEED90 v1.1)

We describe a FORTRAN-90 program to compute low-energy electron diffraction I(V) curves. Plane-waves and layer doubling are used to compute the inter-layer multiple-scattering, while the intra-layer multiple-scattering is computed in the standard way expanding the wavefield on a basis of spherical waves. The program is kept as general as possible, in order to allow testing different parts of multiple-scattering calculations. In particular, it can handle non-diagonal t-matrices describing the scattering of non-spherical potentials, anisotropic vibrations, anharmonicity, etc. The program does not use old FORTRAN flavours, and has been written keeping in mind the advantage for parallelism brought forward by FORTRAN-90.

Regional changes in wind energy potential over Europe using regional climate model ensemble projections

The impact of climate change on wind power generation potentials over Europe is investigated by considering ensemble projections from two regional climate models (RCMs) driven by a global climate model (GCM). Wind energy density and its interannual variability are estimated based on hourly near-surface wind speeds. Additionally, the possible impact of climatic changes on the energy output of a sample 2.5-MW turbine is discussed. GCM-driven RCM simulations capture the behavior and variability of current wind energy indices, even though some differences exist when compared with reanalysis-driven RCM simulations. Toward the end of the twenty-first century, projections show significant changes of energy density on annual average across Europe that are substantially stronger in seasonal terms. The emergence time of these changes varies from region to region and season to season, but some long-term trends are already statistically significant in the middle of the twenty-first century. Over northern and central Europe, the wind energy potential is projected to increase, particularly in winter and autumn. In contrast, energy potential over southern Europe may experience a decrease in all seasons except for the Aegean Sea. Changes for wind energy output follow the same patterns but are of smaller magnitude. The GCM/RCM model chains project a significant intensification of both interannual and intra-annual variability of energy density over parts of western and central Europe, thus imposing new challenges to a reliable pan-European energy supply in future decades.

Conservation laws and tachyon potentials in the sliver frame

Conservation laws have provided an elegant and efficient tool to evaluate the open string field theory interaction vertex, they have been originally implemented in the case where the string field is expanded in the Virasoro basis. In this work we derive conservation laws in the case where the string field is expanded in the so-called sliver L(0)-basis. As an application of this new set of conservation laws, we compute the open string field action relevant to the tachyon condensation and in order to present not only an illustration but also an additional information, we evaluate the action without imposing a gauge choice.

CARBON CREDITS AND ENERGY EFFICIENCY

International carbon credit markets are based in differences between developing and developed countries greenhouse gases emissions mitigation costs and technological limits faced by developed countries. Potential of energy efficiency measures to reduce fossil fuel usage in Brazilian industrial segments is assessed, and analysis of such potentials singles out those segments and regions more apt to generate carbon credits through Clean Development Mechanism (CDM) projects. Though there are currently few Brazilian CDM projects, their number may be significantly increased, which is a positive outcome. For this purpose, it is crucial that energy conservation programs estimate how CDM may improve their economic competitiveness.