A formulação ab-initio da segunda lei da termodinâmica

This paper deals with Carathédory's formulation of the second law of thermodynamics. The material is presented in a didatical way, which allows a second year undergraduate student to follow the formalism. An application is made to an ideal gas with two independent variables. A criticism to Carnot formulation of the second law and an investigation of the historical origins of the Carathéodory formalism are also presented.

Termodinâmica estatística de líquidos com o método de Monte Carlo. I. Metodologia

Statistical mechanics Monte Carlo simulation is reviewed as a formalism to study thermodynamic properties of liquids. Considering the importance of free energy changes in chemical processes, the thermodynamic perturbation theory implemented in the Monte Carlo method is discussed. The representation of molecular interaction by the Lennard-Jones and Coulomb potential functions is also discussed. Charges derived from quantum molecular electrostatic potential are also discussed as an useful methodology to generate an adequate set of partial charges to be used in liquid simulation.

Vacancy-assisted domain-growth in asymmetric binary alloys: A Monte Carlo Study

A Monte Carlo simulation study of the vacancy-assisted domain growth in asymmetric binary alloys is presented. The system is modeled using a three-state ABV Hamiltonian which includes an asymmetry term. Our simulated system is a stoichiometric two-dimensional binary alloy with a single vacancy which evolves according to the vacancy-atom exchange mechanism. We obtain that, compared to the symmetric case, the ordering process slows down dramatically. Concerning the asymptotic behavior it is algebraic and characterized by the Allen-Cahn growth exponent x51/2. The late stages of the evolution are preceded by a transient regime strongly affected by both the temperature and the degree of asymmetry of the alloy. The results are discussed and compared to those obtained for the symmetric case.

Prediction of Antibacterial Activity from Physicochemical Properties of Antimicrobial Peptides

Consensus is gathering that antimicrobial peptides that exert their antibacterial action at the membrane level must reach a local concentration threshold to become active. Studies of peptide interaction with model membranes do identify such disruptive thresholds but demonstrations of the possible correlation of these with the in vivo onset of activity have only recently been proposed. In addition, such thresholds observed in model membranes occur at local peptide concentrations close to full membrane coverage. In this work we fully develop an interaction model of antimicrobial peptides with biological membranes; by exploring the consequences of the underlying partition formalism we arrive at a relationship that provides antibacterial activity prediction from two biophysical parameters: the affinity of the peptide to the membrane and the critical bound peptide to lipid ratio. A straightforward and robust method to implement this relationship, with potential application to high-throughput screening approaches, is presented and tested. In addition, disruptive thresholds in model membranes and the onset of antibacterial peptide activity are shown to occur over the same range of locally bound peptide concentrations (10 to 100 mM), which conciliates the two types of observations

Índices de reatividade química a partir da teoria do funcional de densidade: formalismo e perspectivas

The fundaments of the modern Density Functional Theory (DFT), its basic theorems, principles and methodology are presented. This review also discuss important and widely used concepts in chemistry but that had not been precisely defined until the development of the DFT. These concepts were proposed and used from an empirical base, but now their precise definition are well established in the DFT formalism. Concepts such as chemical potential (electronegativity), hardness, softness and Fukui function are presented and their consequences to the understanding of chemical reactivity are discussed.

Conservation Laws in Cellular Automata

Conservation laws in physics are numerical invariants of the dynamics of a system. In cellular automata (CA), a similar concept has already been defined and studied. To each local pattern of cell states a real value is associated, interpreted as the “energy” (or “mass”, or . . . ) of that pattern.The overall “energy” of a configuration is simply the sum of the energy of the local patterns appearing on different positions in the configuration. We have a conservation law for that energy, if the total energy of each configuration remains constant during the evolution of the CA. For a given conservation law, it is desirable to find microscopic explanations for the dynamics of the conserved energy in terms of flows of energy from one region toward another. Often, it happens that the energy values are from non-negative integers, and are interpreted as the number of “particles” distributed on a configuration. In such cases, it is conjectured that one can always provide a microscopic explanation for the conservation laws by prescribing rules for the local movement of the particles. The onedimensional case has already been solved by Fuk´s and Pivato. We extend this to two-dimensional cellular automata with radius-0,5 neighborhood on the square lattice. We then consider conservation laws in which the energy values are chosen from a commutative group or semigroup. In this case, the class of all conservation laws for a CA form a partially ordered hierarchy. We study the structure of this hierarchy and prove some basic facts about it. Although the local properties of this hierarchy (at least in the group-valued case) are tractable, its global properties turn out to be algorithmically inaccessible. In particular, we prove that it is undecidable whether this hierarchy is trivial (i.e., if the CA has any non-trivial conservation law at all) or unbounded. We point out some interconnections between the structure of this hierarchy and the dynamical properties of the CA. We show that positively expansive CA do not have non-trivial conservation laws. We also investigate a curious relationship between conservation laws and invariant Gibbs measures in reversible and surjective CA. Gibbs measures are known to coincide with the equilibrium states of a lattice system defined in terms of a Hamiltonian. For reversible cellular automata, each conserved quantity may play the role of a Hamiltonian, and provides a Gibbs measure (or a set of Gibbs measures, in case of phase multiplicity) that is invariant. Conversely, every invariant Gibbs measure provides a conservation law for the CA. For surjective CA, the former statement also follows (in a slightly different form) from the variational characterization of the Gibbs measures. For one-dimensional surjective CA, we show that each invariant Gibbs measure provides a conservation law. We also prove that surjective CA almost surely preserve the average information content per cell with respect to any probability measure.

Dependência das vias de dissociação unimolecular com a energia interna da molécula de éter dimetílico

Internal energy dependence of the competitive unimolecular dissociation channels of dimethyl ether were studied with the statistical RRKM formalism. The C-O and C-H fission reactions and the 1,2-H and 1,3-H shifts, and 1,1-H2 and 1,3-H2 molecular eliminations are discussed as a function of energy dependence of k a(E*), the microcanonical rate constant for production of transition states. C-O fission is the dominant process while reaction channels involving C-H fission, 1,1-H2 and 1,3-H2 elimination and production of MeOH should be competitive at energies around 400 kJ mol-1. The less favorable process is the channel of CH4 formation.

Model for interevent times with long tails and multifractality in human communications: An application to financial trading

Social, technological, and economic time series are divided by events which are usually assumed to be random, albeit with some hierarchical structure. It is well known that the interevent statistics observed in these contexts differs from the Poissonian profile by being long-tailed distributed with resting and active periods interwoven. Understanding mechanisms generating consistent statistics has therefore become a central issue. The approach we present is taken from the continuous-time random-walk formalism and represents an analytical alternative to models of nontrivial priority that have been recently proposed. Our analysis also goes one step further by looking at the multifractal structure of the interevent times of human decisions. We here analyze the intertransaction time intervals of several financial markets. We observe that empirical data describe a subtle multifractal behavior. Our model explains this structure by taking the pausing-time density in the form of a superstatistics where the integral kernel quantifies the heterogeneous nature of the executed tasks. A stretched exponential kernel provides a multifractal profile valid for a certain limited range. A suggested heuristic analytical profile is capable of covering a broader region.

Formal Power Analysis of Systems-on-Chip

The design methods and languages targeted to modern System-on-Chip designs are facing tremendous pressure of the ever-increasing complexity, power, and speed requirements. To estimate any of these three metrics, there is a trade-off between accuracy and abstraction level of detail in which a system under design is analyzed. The more detailed the description, the more accurate the simulation will be, but, on the other hand, the more time consuming it will be. Moreover, a designer wants to make decisions as early as possible in the design flow to avoid costly design backtracking. To answer the challenges posed upon System-on-chip designs, this thesis introduces a formal, power aware framework, its development methods, and methods to constraint and analyze power consumption of the system under design. This thesis discusses on power analysis of synchronous and asynchronous systems not forgetting the communication aspects of these systems. The presented framework is built upon the Timed Action System formalism, which offer an environment to analyze and constraint the functional and temporal behavior of the system at high abstraction level. Furthermore, due to the complexity of System-on-Chip designs, the possibility to abstract unnecessary implementation details at higher abstraction levels is an essential part of the introduced design framework. With the encapsulation and abstraction techniques incorporated with the procedure based communication allows a designer to use the presented power aware framework in modeling these large scale systems. The introduced techniques also enable one to subdivide the development of communication and computation into own tasks. This property is taken into account in the power analysis part as well. Furthermore, the presented framework is developed in a way that it can be used throughout the design project. In other words, a designer is able to model and analyze systems from an abstract specification down to an implementable specification.

Sobre a força de ácidos e bases: algumas considerações

This article intends to answer the question: "what is the best way to evaluate the strength of acids and bases?" The meaning of the word strength, the main acid-base theories (ionotropic and electron pair), the neutralization reactions and the thermodynamical formalism are considered. Some cases are presented and discussed. In conclusion, evaluating acid-base strength is dependent on the theory (formalism) as well as on the system and measuring techniques.

Adsorción física sobre sólidos: aspectos termodinámicos

A thermodynamic formalism based on the Gibbs Dividing Surface (GDS) for the description of a solid-fluid interface is presented, so that the adsorption layer is understand as a phase and the adsorption process as the transference of components between a 3-dimensional phase and a 2-dimensional one. Using a state equation derived from the Henry's Law, we shall show how the Langmuir isotherm is deduced from de Gibbs isotherm. The GDS is useful also for understanding the release of heat by a system as the adsorption occurs.

Estudo teórico da estrutura eletrônica e da dinâmica induzida por lasers da molécula de HCl

Potential energy and dipole moment curves for the HCl molecule were computed. Calculations were performed at different levels of theory (DFT, MRCI). Spectroscopic properties are reported and compared with experimental data, for validating the theoretical approaches. Interaction of infrared radiation with HCl is simulated using the wave packet formalism. The quantum control model for population dynamics of the vibrational levels, based on pi-pulse theory, is applied. The results demonstrate that wavepackets with specific composition can be built with short infrared laser pulses and provide the basis for studies of H + HCl collision dynamics with infrared laser excitation.

Simulação de sinais de RMN através das equações de Bloch

The aim of this paper was to present a simple and fast way of simulating Nuclear Magnetic Resonance signals using the Bloch equations. These phenomenological equations describe the classical behavior of macroscopic magnetization and are easily simulated using rotation matrices. Many NMR pulse sequences can be simulated with this formalism, allowing a quantitative description of the influence of many experimental parameters. Finally, the paper presents simulations of conventional sequences such as Single Pulse, Inversion Recovery, Spin Echo and CPMG.

Solving Schrödinger equation for two dimensional potentials using supersymmetry

The formalism of supersymmetric Quantum Mechanics can be extended to arbitrary dimensions. We introduce this formalism and explore its utility to solve the Schrödinger equation for a bidimensinal potential. This potential can be applied in several systems in physical and chemistry context , for instance, it can be used to study benzene molecule.

Towards input/output-free modelling of linear infinite-dimensional systems in continuous time

This dissertation describes a networking approach to infinite-dimensional systems theory, where there is a minimal distinction between inputs and outputs. We introduce and study two closely related classes of systems, namely the state/signal systems and the port-Hamiltonian systems, and describe how they relate to each other. Some basic theory for these two classes of systems and the interconnections of such systems is provided. The main emphasis lies on passive and conservative systems, and the theoretical concepts are illustrated using the example of a lossless transfer line. Much remains to be done in this field and we point to some directions for future studies as well.