Search results for "Gibbs"
showing 10 items of 164 documents
Are one-step aromatic nucleophilic substitutions of non-activated benzenes concerted processes?
2019
Aromatic nucleophilic substitution (SNAr) reactions of non-electrophilically activated benzenes have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP/6-311+G(d) computational level. These reactions, taking place through a one-step mechanism, present a high activation Gibbs free energy, ΔG≠ = 31.0 kcal mol-1, which decreases to 22.1 kcal mol-1 in the intramolecular process. A topological analysis of the electron localisation function along the reaction paths permits establishing the non-concerted nature of these SNAr reactions. A series of unstable structures, with similar electronic structures to those of Meisenheimer intermediates, are characterised. The presen…
A molecular electron density theory study of the [3 + 2] cycloaddition reaction of nitrones with strained allenes
2017
Indexación: Scopus. The [3 + 2] cycloaddition (32CA) reaction of C-phenyl-N-tert-butylnitrone with 1,2-cyclohexadiene (CHDE), a strained allene, has been studied within Molecular Electron Density Theory (MEDT) at the DFT B3LYP/6-311G(d,p) computational level. This non-polar 32CA reaction, which takes place through a non-concerted two-stage one-step mechanism, proceeds with a moderate Gibbs free activation energy of 22.7 kcal mol-1, and presents low stereo- and regioselectivities. The reaction begins by the creation of a pseudoradical center at the central carbon of the strained allene with a relatively low energy cost, which immediately promotes the formation the first C-C single bond. This…
Spatial pattern analysis using hybrid models: an application to the Hellenic seismicity
2016
Earthquakes are one of the most destructive natural disasters and the spatial distribution of their epi- centres generally shows diverse interaction structures at different spatial scales. In this paper, we use a multi-scale point pattern model to describe the main seismicity in the Hellenic area over the last 10 years. We analyze the interaction between events and the relationship with geo- logical information of the study area, using hybrid models as proposed by Baddeley et al. ( 2013 ). In our analysis, we find two competing suitable hybrid models, one with a full parametric structure and the other one based on nonpara- metric kernel estimators for the spatial inhomogeneity.
A molecular electron density theory study of the insertion of CO into frustrated Lewis pair boron-amidines: a [4 + 1] cycloaddition reaction
2019
The insertion of CO into hydrogenated boron-amidine 1 yielding five-membered diazaborolone (5DAB) 3 has been studied within the molecular electron density theory (MEDT) at the DFT ωB97X-D/6-311G(d,p) level. This is a domino process comprised of two consecutive reactions: (i) the dehydrogenation of 1 yielding the frustrated Lewis pair (FLP) boron-amidine 4, which quickly equilibrates with four-membered diazaborolone (4DAB) 2; and (ii) the addition of CO into FLP 4, yielding the final 5DAB 3. Analysis of the Gibbs free energies indicates that the extrusion of H2 demands a high ΔG≠ of 28.6 kcal·mol-1, being endergonic by 6.7 kcal·mol-1. The subsequent addition of CO into FLP 4 presents a low Δ…
Unveiling the Intramolecular Ionic Diels–Alder Reactions within Molecular Electron Density Theory
2021
The intramolecular ionic Diels–Alder (IIDA) reactions of two dieniminiums were studied within the Molecular Electron Density Theory (MEDT) at the ωB97XD/6-311G(d,p) computational level. Topological analysis of the electron localization function (ELF) of dieniminiums showed that their electronic structures can been seen as the sum of those of butadiene and ethaniminium. The superelectrophilic character of dieniminiums accounts for the high intramolecular global electron density transfer taking place from the diene framework to the iminium one at the transition state structures (TSs) of these IIDA reactions, which are classified as the forward electro density flux. The activation enthalpy ass…
Adaptive independent sticky MCMC algorithms
2018
In this work, we introduce a novel class of adaptive Monte Carlo methods, called adaptive independent sticky MCMC algorithms, for efficient sampling from a generic target probability density function (pdf). The new class of algorithms employs adaptive non-parametric proposal densities which become closer and closer to the target as the number of iterations increases. The proposal pdf is built using interpolation procedures based on a set of support points which is constructed iteratively based on previously drawn samples. The algorithm's efficiency is ensured by a test that controls the evolution of the set of support points. This extra stage controls the computational cost and the converge…
The Recycling Gibbs sampler for efficient learning
2018
Monte Carlo methods are essential tools for Bayesian inference. Gibbs sampling is a well-known Markov chain Monte Carlo (MCMC) algorithm, extensively used in signal processing, machine learning, and statistics, employed to draw samples from complicated high-dimensional posterior distributions. The key point for the successful application of the Gibbs sampler is the ability to draw efficiently samples from the full-conditional probability density functions. Since in the general case this is not possible, in order to speed up the convergence of the chain, it is required to generate auxiliary samples whose information is eventually disregarded. In this work, we show that these auxiliary sample…
Grapham: Graphical models with adaptive random walk Metropolis algorithms
2008
Recently developed adaptive Markov chain Monte Carlo (MCMC) methods have been applied successfully to many problems in Bayesian statistics. Grapham is a new open source implementation covering several such methods, with emphasis on graphical models for directed acyclic graphs. The implemented algorithms include the seminal Adaptive Metropolis algorithm adjusting the proposal covariance according to the history of the chain and a Metropolis algorithm adjusting the proposal scale based on the observed acceptance probability. Different variants of the algorithms allow one, for example, to use these two algorithms together, employ delayed rejection and adjust several parameters of the algorithm…
A multi-scale area-interaction model for spatio-temporal point patterns
2018
Models for fitting spatio-temporal point processes should incorporate spatio-temporal inhomogeneity and allow for different types of interaction between points (clustering or regularity). This paper proposes an extension of the spatial multi-scale area-interaction model to a spatio-temporal framework. This model allows for interaction between points at different spatio-temporal scales and the inclusion of covariates. We fit the proposed model to varicella cases registered during 2013 in Valencia, Spain. The fitted model indicates small scale clustering and regularity for higher spatio-temporal scales.
Gibbs and harmonic measures for foliations with negatively curved leaves
2013
In this thesis we develop a notion of Gibbs measure for the geodesic flow tangent to a foliated bundle over a compact and negatively curved basis. We also develop a notion of F-harmonic measure and prove that there exists a natural bijective correspondence between the two. For projective foliated bundles with sphere-fibers without transverse invariant measure, we show the uniqueness of these measures for any Hölder potential on the basis. In that case we also prove that F-harmonic measures are realized as weighted limits of large balls tangent to the leaves and that their conditional measures on the fibers are limits of weighted averages on the orbits of the holonomy group.