Application of a generalized thermodynamic approach to characterize mesoporous materials

Equilibrium adsorption and desorption in mesoporous adsorbents is considered on the basis of rigorous thermodynamic analysis, in which the curvature-dependent solid-fluid potential and the compressibility of the adsorbed phase are accounted for. The compressibility of the adsorbed phase is considered for the first time in the literature in the framework of a rigorous thermodynamic approach. Our model is a further development of continuum thermodynamic approaches proposed by Derjaguin and Broekhoff and de Boer, and it is based on a reference isotherm of a non-porous material having the same chemical structure as that of the pore wall. In this improved thermodynamic model, we incorporated a prescription for transforming the solid-fluid potential exerted by the flat reference surface to the potential inside cylindrical and spherical pores. We relax the assumption that the adsorbed film density is constant and equal to that of the saturated liquid. Instead, the density of the adsorbed fluid is allowed to vary over the adsorbed film thickness and is calculated by an equation of state. As a result, the model is capable to describe the adsorption-desorption reversibility in cylindrical pores having diameter less than 2 nm. The generalized thermodynamic model may be applied to the pore size characterization of mesoporous materials instead of much more time-consuming molecular approaches. (c) 2005 Elsevier B.V. All rights reserved.

Quantum entanglement in the two-impurity Kondo model

In order to quantify quantum entanglement in two-impurity Kondo systems, we calculate the concurrence, negativity, and von Neumann entropy. The entanglement of the two Kondo impurities is shown to be determined by two competing many-body effects, namely the Kondo effect and the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction, I. Due to the spin-rotational invariance of the ground state, the concurrence and negativity are uniquely determined by the spin-spin correlation between the impurities. It is found that there exists a critical minimum value of the antiferromagnetic correlation between the impurity spins which is necessary for entanglement of the two impurity spins. The critical value is discussed in relation with the unstable fixed point in the two-impurity Kondo problem. Specifically, at the fixed point there is no entanglement between the impurity spins. Entanglement will only be created [and quantum information processing (QIP) will only be possible] if the RKKY interaction exchange energy, I, is at least several times larger than the Kondo temperature, T-K. Quantitative criteria for QIP are given in terms of the impurity spin-spin correlation.

Transition in convective flows heated internally

The stability of internally heated convective flows in a vertical channel under the influence of a pressure gradient and in the limit of small Prandtl number is examined numerically. In each of the cases studied the basic flow, which can have two inflection points, loses stability at the critical point identified by the corresponding linear analysis to two-dimensional states in a Hopf bifurcation. These marginal points determine the linear stability curve that identifies the minimum Grashof number (based on the strength of the homogeneous heat source), at which the two-dimensional periodic flow can bifurcate. The range of stability of the finite amplitude secondary flow is determined by its (linear) stability against three-dimensional infinitesimal disturbances. By first examining the behavior of the eigenvalues as functions of the Floquet parameters in the streamwise and spanwise directions we show that the secondary flow loses stability also in a Hopf bifurcation as the Grashof number increases, indicating that the tertiary flow is quasi-periodic. Secondly the Eckhaus marginal stability curve, that bounds the domain of stable transverse vortices towards smaller and larger wavenumbers, but does not cause a transition as the Grashof number increases, is also given for the cases studied in this work.

Typical case behaviour of spin systems in random graph and composite ensembles

This thesis includes analysis of disordered spin ensembles corresponding to Exact Cover, a multi-access channel problem, and composite models combining sparse and dense interactions. The satisfiability problem in Exact Cover is addressed using a statistical analysis of a simple branch and bound algorithm. The algorithm can be formulated in the large system limit as a branching process, for which critical properties can be analysed. Far from the critical point a set of differential equations may be used to model the process, and these are solved by numerical integration and exact bounding methods. The multi-access channel problem is formulated as an equilibrium statistical physics problem for the case of bit transmission on a channel with power control and synchronisation. A sparse code division multiple access method is considered and the optimal detection properties are examined in typical case by use of the replica method, and compared to detection performance achieved by interactive decoding methods. These codes are found to have phenomena closely resembling the well-understood dense codes. The composite model is introduced as an abstraction of canonical sparse and dense disordered spin models. The model includes couplings due to both dense and sparse topologies simultaneously. The new type of codes are shown to outperform sparse and dense codes in some regimes both in optimal performance, and in performance achieved by iterative detection methods in finite systems.

Temporal correlations of local network losses

We introduce a continuum model describing data losses in a single node of a packet-switched network (like the Internet) which preserves the discrete nature of the data loss process. By construction, the model has critical behavior with a sharp transition from exponentially small to finite losses with increasing data arrival rate. We show that such a model exhibits strong fluctuations in the loss rate at the critical point and non-Markovian power-law correlations in time, in spite of the Markovian character of the data arrival process. The continuum model allows for rather general incoming data packet distributions and can be naturally generalized to consider the buffer server idleness statistics.

Loss fluctuations and temporal correlations in network queues

We consider data losses in a single node of a packet- switched Internet-like network. We employ two distinct models, one with discrete and the other with continuous one-dimensional random walks, representing the state of a queue in a router. Both models have a built-in critical behavior with a sharp transition from exponentially small to finite losses. It turns out that the finite capacity of a buffer and the packet-dropping procedure give rise to specific boundary conditions which lead to strong loss rate fluctuations at the critical point even in the absence of such fluctuations in the data arrival process.

Random walks in local dynamics of network losses

We suggest a model for data losses in a single node (memory buffer) of a packet-switched network (like the Internet) which reduces to one-dimensional discrete random walks with unusual boundary conditions. By construction, the model has critical behavior with a sharp transition from exponentially small to finite losses with increasing data arrival rate. We show that for a finite-capacity buffer at the critical point the loss rate exhibits strong fluctuations and non-Markovian power-law correlations in time, in spite of the Markovian character of the data arrival process.

Fluctuations and correlations in sandpiles and interfaces with boundary pinning

Interfaces are studied in an inhomogeneous critical state where boundary pinning is compensated with a ramped force. Sandpiles driven off the self-organized critical point provide an example of this ensemble in the Edwards-Wilkinson (EW) model of kinetic roughening. A crossover from quenched to thermal noise violates spatial and temporal translational invariances. The bulk temporal correlation functions have the effective exponents β1D∼0.88±0.03 and β2D∼0.52±0.05, while at the boundaries βb,1D/2D∼0.47±0.05. The bulk β1D is shown to be reproduced in a randomly kicked thermal EW model.

Fluctuations and correlations in sandpiles and interfaces with boundary pinning

Interfaces are studied in an inhomogeneous critical state where boundary pinning is compensated with a ramped force. Sandpiles driven off the self-organized critical point provide an example of this ensemble in the Edwards-Wilkinson (EW) model of kinetic roughening. A crossover from quenched to thermal noise violates spatial and temporal translational invariances. The bulk temporal correlation functions have the effective exponents β1D∼0.88±0.03 and β2D∼0.52±0.05, while at the boundaries βb,1D/2D∼0.47±0.05. The bulk β1D is shown to be reproduced in a randomly kicked thermal EW model.

Cerami (C) Condition and Mountain Pass Theorem for Multivalued Mappings

Partially supported by Sapientia Foundation.

On a Variational Approach to some Quasilinear Problems

We prove some multiplicity results concerning quasilinear elliptic equations with natural growth conditions. Techniques of nonsmooth critical point theory are employed.

Nontrivial Solutions of Quasilinear Equations In BV

The existence of a nontrivial critical point is proved for a functional containing an area-type term. Techniques of nonsmooth critical point theory are applied.

On a Class of Elliptic Equations for the N-Laplacian in R^n with One-Sided Exponential Growth

2000 Mathematics Subject Classification: 35J40, 49J52, 49J40, 46E30

Estudo sobre a detecção de invariância de escala discreta em sistemas com criticalidade auto-organizada

Recent studies have shown evidence of log-periodic behavior in non-hierarchical systems. An interesting fact is the emergence of such properties on rupture and breakdown of complex materials and financial failures. These may be examples of systems with self-organized criticality (SOC). In this work we study the detection of discrete scale invariance or log-periodicity. Theoretically showing the effectiveness of methods based on the Fourier Transform of the log-periodicity detection not only with prior knowledge of the critical point before this point as well. Specifically, we studied the Brazilian financial market with the objective of detecting discrete scale invariance in Bovespa (Bolsa de Valores de S˜ao Paulo) index. Some historical series were selected periods in 1999, 2001 and 2008. We report evidence for the detection of possible log-periodicity before breakage, shown its applicability to the study of systems with discrete scale invariance likely in the case of financial crashes, it shows an additional evidence of the possibility of forecasting breakage

Estudo da transição de fase da percolação através da entropia da informação

Various physical systems have dynamics that can be modeled by percolation processes. Percolation is used to study issues ranging from fluid diffusion through disordered media to fragmentation of a computer network caused by hacker attacks. A common feature of all of these systems is the presence of two non-coexistent regimes associated to certain properties of the system. For example: the disordered media can allow or not allow the flow of the fluid depending on its porosity. The change from one regime to another characterizes the percolation phase transition. The standard way of analyzing this transition uses the order parameter, a variable related to some characteristic of the system that exhibits zero value in one of the regimes and a nonzero value in the other. The proposal introduced in this thesis is that this phase transition can be investigated without the explicit use of the order parameter, but rather through the Shannon entropy. This entropy is a measure of the uncertainty degree in the information content of a probability distribution. The proposal is evaluated in the context of cluster formation in random graphs, and we apply the method to both classical percolation (Erd¨os- R´enyi) and explosive percolation. It is based in the computation of the entropy contained in the cluster size probability distribution and the results show that the transition critical point relates to the derivatives of the entropy. Furthermore, the difference between the smooth and abrupt aspects of the classical and explosive percolation transitions, respectively, is reinforced by the observation that the entropy has a maximum value in the classical transition critical point, while that correspondence does not occurs during the explosive percolation.