Constructing Mixed Density Functionals for Describing Dissociative Chemisorption on Metal Surfaces: Basic Principles.

The production of a majority of chemicals involves heterogeneous catalysis at some stage, and the rates of many heterogeneously catalyzed processes are governed by transition states for dissociative chemisorption on metals. Accurate values of barrier heights for dissociative chemisorption on metals are therefore important to benchmarking electronic structure theory in general and density functionals in particular. Such accurate barriers can be obtained using the semiempirical specific reaction parameter (SRP) approach to density functional theory. However, this approach has thus far been rather ad hoc in its choice of the generic expression of the SRP functional to be used, and there is a need for better heuristic approaches to determining the mixing parameters contained in such expressions. Here we address these two issues. We investigate the ability of several mixed, parametrized density functional expressions combining exchange at the generalized gradient approximation (GGA) level with either GGA or nonlocal correlation to reproduce barrier heights for dissociative chemisorption on metal surfaces. For this, seven expressions of such mixed density functionals are tested on a database consisting of results for 16 systems taken from a recently published slightly larger database called SBH17. Three expressions are derived that exhibit high tunability and use correlation functionals that are either of the PBE GGA form or of one of two limiting nonlocal forms also describing the attractive van der Waals interaction in an approximate way. We also find that, for mixed density functionals incorporating GGA correlation, the optimum fraction of repulsive RPBE GGA exchange obtained with a specific GGA density functional is correlated with the charge-transfer parameter, which is equal to the difference in the work function of the metal surface and the electron affinity of the molecule. However, the correlation is generally not large and not large enough to obtain accurate guesses of the mixing parameter for the systems considered, suggesting that it does not give rise to a very effective search strategy.

Contactless radar-based breathing monitoring of premature infants in the neonatal intensive care unit.

Vital sign monitoring systems are essential in the care of hospitalized neonates. Due to the immaturity of their organs and immune system, premature infants require continuous monitoring of their vital parameters and sensors need to be directly attached to their fragile skin. Besides mobility restrictions and stress, these sensors often cause skin irritation and may lead to pressure necrosis. In this work, we show that a contactless radar-based approach is viable for breathing monitoring in the Neonatal intensive care unit (NICU). For the first time, different scenarios common to the NICU daily routine are investigated, and the challenges of monitoring in a real clinical setup are addressed through different contributions in the signal processing framework. Rather than just discarding measurements under strong interference, we present a novel random body movement mitigation technique based on the time-frequency decomposition of the recovered signal. In addition, we propose a simple and accurate frequency estimator which explores the harmonic structure of the breathing signal. As a result, the proposed radar-based solution is able to provide reliable breathing frequency estimation, which is close to the reference cabled device values most of the time. Our findings shed light on the strengths and limitations of this technology and lay the foundation for future studies toward a completely contactless solution for vital signs monitoring.

On the Analysis of PM/FM Noise Radar Waveforms Considering Modulating Signals with Varied Stochastic Properties.

Noise Radar technology is the general term used to describe radar systems that employ realizations of a given stochastic process as transmit waveforms. Originally, carriers modulated in amplitude by a Gaussian random signal, derived from a hardware noise source, were taken into consideration, justifying the adopted nomenclature. With the advances made in hardware as well as the rise of the software defined noise radar concept, waveform design emerges as an important research area related to such systems. The possibility of generating signals with varied stochastic properties increased the potential in achieving systems with enhanced performances. The characterization of random phase and frequency modulated waveforms (more suitable for several applications) has then gained considerable notoriety within the radar community as well. Several optimization algorithms have been proposed in order to conveniently shape both the autocorrelation function of the random samples that comprise the transmit signal, as well as their power spectrum density. Nevertheless, little attention has been driven to properly characterize the stochastic properties of those signals through closed form expressions, jeopardizing the effectiveness of the aforementioned algorithms as well as their reproducibility. Within this context, this paper investigates the performance of several random phase and frequency modulated waveforms, varying the stochastic properties of their modulating signals.

Effects of riparian vegetation on the structure of the marginal aquatic habitat and the associated fish assemblage in a tropical Brazilian reservoir / Efeitos da cobertura vegetal ripária na estrutura do habitat aquático marginal e na fauna de peixes associada em um reservatório tropical brasileiro

Riparian zones represent areas of strong biological, physical and chemical interaction between terrestrial and aquatic ecosystems. These areas are usually typified by high diversity of fauna, flora and environmental processes. The present study evaluates the littoral habitat structure and its fish fauna related to associations between presence and absence of natural riparian vegetal cover, in a reservoir in northeastern Brazil. Sampling was performed on marginal areas where riparian vegetation was present and where it had been removed for the plantation of sugar cane. For each type of marginal area three replicate sites were sampled during the wet season. Data on the habitat structure (submerged elements and substrate composition), fish and water quality were collected. The data was analyzed using Shannon-Wiener's diversity index and Pielou's equitability. Non-metric Multidimensional Scaling and the Multi-Response Permutation Procedure were used to evaluate similarities between sites. The structure of the habitat was more diverse in sites were natural riparian vegetation was still present. Muddy substrate was more abundant in areas with riparian vegetation whereas sandy substrate was more abundant in areas where riparian vegetation had been removed. Measured physico-chemical parameters and nutrients remained nearly constant across all sites. Metynnis lippincottianus and Crenicichla menezesi were more associated with the habitat in areas where riparian vegetation was removed, whereas Cichlasoma orientale and Cichla ocellaris were strongly correlated to forested areas.

A zona ripária representa uma área de importantes interações, sejam biológicas, físicas ou químicas, entre o ecossistema terrestre e aquático. Essas áreas são geralmente caracterizadas por uma alta diversidade de fauna, flora e processos ecológicos. Este estudo avalia a estrutura do habitat aquático e a fauna de peixes com relação à presença e ausência da mata ciliar natural em um reservatório no Nordeste brasileiro. Amostragens foram realizadas em áreas marginais onde a mata ciliar estava presente e onde esta havia sido removida para o plantio de cana-de-açúcar. Em cada área, três pontos de coleta foram amostrados durante o período chuvoso. Dados sobre a estrutura do habitat (elementos submersos e composição do substrato), peixes e qualidade da água foram coletados. Os dados foram analisados usando o índice de diversidade de Shannon-Wiener e a equitabilidade de Pielou. Escalonamento multidimensional não métrico associado a um procedimento de permutações multiplas foi usado para avaliar as similaridades entre os pontos de coleta. A estrutura do habitat mostrou-se mais diversa em locais onde a mata ciliar não havia sido removida. Lama foi o tipo de substrato mais abundante em áreas onde a mata ciliar esteve intacta, enquanto que areia foi o tipo de substrato mais comum em áreas onde a mata ciliar foi removida. Variáveis físico-químicas e nutrientes dissolvidos na água apresentaram valores relativamente constantes em todos os locais estudados. Metynnis lippincottianus e Crenicichla menezesi estiveram associados com áreas onde a mata ciliar foi removida, enquanto Cichlasoma orientale e Cichla ocellaris estiveram mais fortemente correlacionados com áreas onde a mata ciliar estava preservada.