The effect of concentration on the Surface-Enhanced Raman Scattering of p-Aminothiophenol

The organic compound p-aminothiophenol (pATP, HS-Ph-NH2) has become very popular because it is often used for checking the enhancement capability of each new SERS substrate due to its very intense SERS spectra. SERS of pATP on silver electrode is significantly different from its ordinary Raman spectra and it is very dependent on the particular conditions of the SERS experiment. In this work the effect of adsorbate concentration on the potential dependent SERS spectra of pATP recorded on a silver electrode has been studied using NaClO4 as electrolyte. On the other hand, MS-CASPT2 have been performed in order to help the analysis of the experimental results by computing resonance Raman spectra of selected structural models of the metal−adsorbate surface complex. It is found that the spectra are dependent on adsorbate concentration and dominated by a resonant charge transfer (CT) mechanism, where the charge is always transferred from the adsorbate to the metal. The relative SERS enhancements are due to Franck−Condon factors related to the CT process, and there are not intensified bands through Herzberg−Teller contributions. Furthermore, the Raman signals of the SERS recorded at low concentration arise from at least three different molecular species: (i) pATP bonded to silver electrode through sulfur atom (Agn-S−-Ph-NH2); (ii) pATP bonded to silver electrode through both sulfur and nitrogen atoms (Agn-S−-PhNH2-Agm); (iii) The azo derivative p,p′-dimercaptoazobenzene (or its nitrene precursor).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Detection of different species of p-aminothiophenol on silver nanoparticles by Surface-Enhanced Raman Spectroscopy (SERS)

In the present work we have analyzed the experimental and theoretical SERS spectra of the organic compound p-aminothiophenol (pATP, HS-Ph-NH2) recorded on silver nanoparticles. DFT calculations have been performed to support the experimental results in order to estimate the adsorption specie and the corresponding Raman bands assignment. It is found a different adsorption behavior of pATP not only by changing the concentration of the adsorbate but also by exciting the sample at different wavelengths.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Temperature inversion in granular fluids under gravity

We study, via hydrodynamic equations, the granular temperature profile of a granular fluid under gravity and subjected to energy injection from a base. It is found that there exists a turn-up in the granular temperature and that, far from the base, it increases linearly with height. We show that this phenomenon, observed previously in experiments and computer simulations, is a direct consequence of the heat flux law, different form Fourier's, in granular fluids. The positive granular temperature gradient is proportional to gravity and a transport coefficient $\mu_0$, relating the heat flux to the density gradients, that is characteristic of granular systems. Our results provide a method to compute the value $\mu_0$ for different restitution coefficients. The theoretical predictions are verified by means of molecular dynamics simulations, and the value of $\mu_0$ is computed for the two dimensional inelastic hard sphere model. We provide, also, a boundary condition for the temperature field that is consistent with the modified Fourier's law.Comment: Submitted to Physica

Razón y Racionalidad. Una Dialéctica de la Modernidad

En este trabajo se discute acerca de la distinción entre razón y racionalidad, pues se le ha colmado con prejuicios, imaginarios y mitos. Sin embargo, la comprensión del concepto de racionalidad lleva a la interpretación moderna del mundo y debido a la conexión entre teoría de la racionalidad y de la modernidad se puede construir una teoría de la sociedad. Para el análisis se recuperan aquellos autores que han enfatizado la ponencia crítica de la razón, para cuestionar como plantea Habermas las aporías de la razón y reivindicar el proyecto emancipador de la propia razón, rescatar el mundo de la vida de la racionalidad instrumental para crear la posibilidad de una sociedad verdaderamente humana

La dialéctica de la calidad universitaria en las políticas de modernización para la educación

El artículo analiza las políticas públicas para la educación superior a partir de las contradicciones y características de los modos de producción material, las transformaciones de las estrategias de acumulación, las crisis y el cambio en las relaciones entre la esfera de lo privado y de lo público. Así, el problema de la calidad de la educación se descubre como una ideología inmersa en esas modificaciones que tienen efectos en lo educativo mediante la conformación de un nuevo proyecto para la universidad pública, que mantiene y reproduce las desigualdades sociales, a través de instituciones de educación superior que tienden a volverse organizaciones elitistas, a la vez que ellas mismas son sometidas a imperativos de una racionalidad instrumental, a través de la estrategia de evaluación que privilegia la selectividad, tanto a nivel del crecimiento de la matrícula como de la asignación de los recursos financieros, por lo que las universidades públicas abandonan su función social y crítica

Correction algorithm for finite sample statistics

Assume in a sample of size M one finds M_i representatives of species i with i=1...N^*. The normalized frequency p^*_i=M_i/M, based on the finite sample, may deviate considerably from the true probabilities p_i. We propose a method to infer rank-ordered true probabilities r_i from measured frequencies M_i. We show that the rank-ordered probabilities provide important informations on the system, e.g., the true number of species, the Shannon- and the Renyi-entropies.Comment: 11 pages, 9 figure

On identifiability of MAP processes

Two types of transitions can be found in the Markovian Arrival process or MAP: with and without arrivals. In transient transitions the chain jumps from one state to another with no arrival; in effective transitions, a single arrival occurs. We assume that in practice, only arrival times are observed in a MAP. This leads us to define and study the Effective Markovian Arrival process or E-MAP. In this work we define identifiability of MAPs in terms of equivalence between the corresponding E-MAPs and study conditions under which two sets of parameters induce identical laws for the observable process, in the case of 2 and 3-states MAP. We illustrate and discuss our results with examples.Batch Markovian Arrival process, Hidden Markov models, Identifiability problems

Non-identifiability of the two state Markovian Arrival process

In this paper we consider the problem of identifiability of the two-state Markovian Arrival process (MAP2). In particular, we show that the MAP2 is not identifiable and conditions are given under which two different sets of parameters, induce identical stationary laws for the observable process.Batch Markovian Arrival process, Markov Renewal process, Hidden Markov models, Identifiability problems

Inference for double Pareto lognormal queues with applications

In this article we describe a method for carrying out Bayesian inference for the double Pareto lognormal (dPlN) distribution which has recently been proposed as a model for heavy-tailed phenomena. We apply our approach to inference for the dPlN/M/1 and M/dPlN/1 queueing systems. These systems cannot be analyzed using standard techniques due to the fact that the dPlN distribution does not posses a Laplace transform in closed form. This difficulty is overcome using some recent approximations for the Laplace transform for the Pareto/M/1 system. Our procedure is illustrated with applications in internet traffic analysis and risk theory.Heavy tails, Bayesian inference, Queueing theory