Anharmonic Vibrational Eigenfunctions and Infrared Spectra from Semiclassical Molecular Dynamics

We describe a new approach based on semiclassical molecular dynamics that allows to simulate infrared absorption or emission spectra of molecular systems with inclusion of anharmonic intensities. This is achieved from semiclassical power spectra by computing first the vibrational eigenfunctions as a linear combination of harmonic states, and then the oscillator strengths associated to the vibrational transitions. We test the approach against a 1D Morse potential and apply it to the water molecule with results in excellent agreement with discrete variable representation quantum benchmarks. The method does not require any grid calculations and it is directly extendable to high dimensional systems. The usual exponential scaling of the basis set size with the dimensionality of the system can be avoided by means of an appropriate truncation scheme. Furthermore, the approach has the advantage to provide IR spectra beyond the harmonic approximation without losing the possibility of an intuitive assignment of absorption peaks in terms of normal modes of vibration

An Effective Semiclassical Approach to IR Spectroscopy

We present a novel approach to calculate molecular IR spectra based on semiclassical molecular dynamics. The main advance from a previous semiclassical method [M. Micciarelli, R. Conte, J. Suarez, M. Ceotto J. Chem. Phys. 149, 064115 (2018)] consists in the possibility to avoid state-to-state calculations making applications to systems characterized by sizable densities of vibrational states feasible. Furthermore, this new method accounts not only for positions and intensities of the several absorption bands which make up the IR spectrum, but also for their shapes. We show that accurate semiclassical IR spectra including quantum effects and anharmonicities for both frequencies and intensities can be obtained starting from semiclassical power spectra. The approach is first tested against the water molecule, and then applied to the 10-atom glycine aminoacid

Artificial diagnosis of sensory taints due to brettanomyces spp. contamination in Valpolicella wines

Diagnosis and intervention to avoid Brett taints in the product can be a time-consuming task for the enologist in large production facilities and an instrumental and automated detection systems assisting the local expert technician would be desirable. This paper investigates whether electronic noses, which have been tested in other wine making and classification tasks, can be of use in detecting Brett taints in Valpolicella wines

A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X -band electron paramagnetic resonance spectroscopy

The effect of cyclones crossing the Mediterranean region on sea level anomalies on the Mediterranean Sea coast

Abstract. Large positive and negative sea level anomalies on the coast of the Mediterranean Sea are linked to intensity and position of cyclones moving along the Mediterranean storm track with dynamics involving different factors. This analysis is based on a model hindcast and considers nine coastal stations, which are representative of sea level anomalies with different magnitudes and characteristics. When a shallow water fetch is present, the wind around the cyclone centre is the main cause of positive and negative sea level anomalies, depending on its onshore or offshore direction. The inverse barometer effect produces a positive anomaly on the coast near the cyclone pressure minimum and a negative anomaly at the opposite side of the Mediterranean Sea. The latter is caused by the cross-basin mean sea level pressure gradient that is associated with the presence of a cyclone. This often coincides with the presence of an anticyclone above the station, which causes a local negative inverse barometer effect. Further, at some stations, negative sea level anomalies are reinforced by a residual water mass redistribution within the basin, which is associated with a transient response to the atmospheric pressure forcing. Though the link with the presence of a cyclone in the Mediterranean has comparable importance for positive and negative anomalies, the relation between cyclone position and intensity is stronger for the magnitude of positive events. The area of cyclogenesis, track of the central minimum and position at the time of the event differ depending on the location the sea level anomaly occurs and on its sign. The western Mediterranean is the main cyclogenesis area for both positive and negative anomalies overall. Atlantic cyclones mainly produce positive sea level anomalies in the western basin. At the easternmost stations, positive anomalies are caused by cyclogenesis in the eastern Mediterranean. North African cyclogenesis is a major source of positive anomalies on the central African coast and negative anomalies on the eastern Mediterranean and northern Aegean coasts

Implicazioni stilistiche della metrica giudiciana: L’enjambement ne La Vita in versi

Mediante l’analisi del ricorso all’enjambement nella raccolta poetica La Vita in versi di Giovanni Giudici, nella valutazione delle sue conseguenze metrico-ritmiche e della sua intensità, e nella descrizione delle sue implicazioni stilistico-espressive, si verifica l’interazione del livello metrico-semantico e del significante poetico nel determinare l’efficacia e la memorabilità dei versi della silloge, uno dei più notevoli episodi di realismo poetico del Novecento italiano.In this article we will analyse the use of the enjambment in the collection of poems by Giovanni Giudici La vita in versi. In particular, we will consider its metric-rhythmic consequences and its intensity and we will analyse its stylistic-expressive implications. This will lead us to verify the interaction of the metric-semantic level and of the poetic signifier in producing the effectiveness and the memorability of the collection, which is one of the most important products of the poetic realism in the Italian Twentieth Cetury.

Walking Through the Method Zoo: Does Higher Education Really Meet Software Industry Demands?

Software engineering educators are continually challenged by rapidly evolving concepts, technologies, and industry demands. Due to the omnipresence of software in a digitalized society, higher education institutions (HEIs) have to educate the students such that they learn how to learn, and that they are equipped with a profound basic knowledge and with latest knowledge about modern software and system development. Since industry demands change constantly, HEIs are challenged in meeting such current and future demands in a timely manner. This paper analyzes the current state of practice in software engineering education. Specifically, we want to compare contemporary education with industrial practice to understand if frameworks, methods and practices for software and system development taught at HEIs reflect industrial practice. For this, we conducted an online survey and collected information about 67 software engineering courses. Our findings show that development approaches taught at HEIs quite closely reflect industrial practice. We also found that the choice of what process to teach is sometimes driven by the wish to make a course successful. Especially when this happens for project courses, it could be beneficial to put more emphasis on building learning sequences with other courses

Estudo numérico e experimental da geração de golfadas em um escoamento bifásico de gás-líquido

Many industrial processes like crude oil transportation in pipelines operate on two-phase flow regime, especially in slug flow pattern. Slug flows are characterized by the intermittent succession of liquid slugs having a large momentum, followed by long bubbles of compressible gas. This kind of flow has been a topic of research over the last decades; however, few mathematical models for this complex flow can be found in the literature. Among those, one might mention the Eulerian two-fluid and drift flux, and the Lagrangian slug-tracking. Based on the work of Renault (2007), this work presents a Lagrangian methodology to capture the process of slug initiation for horizontal and near horizontal pipes. Starting from one dimensional two-fluid model, the equations of momentum and mass conservation were simplified. The motion generated by the dynamic pressure of the gas was decoupled from the slow movement of the liquid film. The resulting system of equations for the gas phase was discretized using the finite difference method and solved with the tri-diagonal matrix algorithm (TDMA). The liquid motion in the bubbles was then modeled by a modified version of shallow water equations. A software using Intel Visual Fortran language to simulate the process of slug initiation in a gas-liquid stratified flow was developed. Wave growth in the liquid-gas interface was numerically monitored until one of those waves reached the top of the pipe to form a slug. Numerical simulations were performed for different gas-liquid flow conditions, in order to evaluate the ability of the model to generate slugs. Experimental data to validate the code were gathered at the experimental facility of NUEM/UTFPR. The data were acquired using two-wire resistive sensors. The numerical results showed to be strongly dependent on mesh size. Because of this, a limiting criterion for the mesh size was developed. The linear analysis showed higher wave growth rate to this model than the two-fluid model. The results showed consistency when compared to the experimental data, especially in the neighborhoods of the region where the model is ill-posed.O escoamento bifásico em golfadas está presente em diversos processos industriais, entre eles a produção e transporte do petróleo. Ele se caracteriza pelo escoamento de um pistão de líquido com grande quantidade de movimento seguido por uma bolha de gás compressível. A repetição destas estruturas ocorre de forma intermitente. Nas últimas décadas, surgiram alguns modelos para a simulação deste tipo de escoamento, como os modelos eulerianos de dois fluidos e drift flux, e lagrangeano de seguimento de pistões (slug tracking). Com base no trabalho de Renault (2007), uma metodologia lagrangeana foi desenvolvida para monitorar e acompanhar o processo de iniciação do escoamento em golfadas em tubulações horizontais e levemente inclinadas de modo autônomo. Partindo-se do modelo de dois fluidos com aproximação unidimensional, as equações de conservação de massa e balanço de quantidade de movimento foram simplificadas. O sistema de equações resultante para o domínio de gás foi discretizado utilizando-se o método de diferenças finitas e resolvido através do algoritmo TDMA. O movimento do líquido sob as bolhas foi modelado de modo semelhante às equações de águas rasas (shallow water equations). Um programa computacional na linguagem Intel Visual Fortran foi desenvolvido para simular o processo de iniciação do escoamento em golfadas, a partir do escoamento estratificado líquido-gás. O crescimento das ondas na interface líquido-gás foi monitorado numericamente, assim como os pistões de líquido que se formaram em decorrência do crescimento das ondas. Foram realizadas simulações numéricas, para diferentes condições de vazão de líquido-gás, com a finalidade de avaliar a capacidade do modelo de gerar pistões. Para a validação dos resultados numéricos, foram realizadas medidas experimentais na bancada de escoamento bifásico existente no NUEM/UTFPR. Os dados foram obtidos utilizando-se sensores resistivos. Foi verificada uma forte dependência dos resultados do modelo em relação à malha. Devido a isto, foi proposto um critério para limitar o refinamento máximo da malha. Uma análise linear levou a conclusão que o modelo apresenta maiores taxas de crescimento de onda em relação ao modelo de dois fluidos. Os resultados numéricos mostraram boa concordância com os dados experimentais, porém apresentam melhor desempenho quando próximos à região onde o modelo se encontra mal posto numericamente

Heterogeneous gold and vanadium based catalysts for hydrochlorination and oxidation reactions.

The first examples of gold as the catalyst of choice were the hydrochlorination of acetylene using gold on carbon catalysts and the oxidation of carbon monoxide, both identified around 20 years ago. From that time most research interest has been focused on the use of gold as a catalyst for oxidation reactions, whereas although gold can be an excellent electrophilic agent is some of its oxidation states, few studies are available which display this. Chlorinated organic compounds are widely manufactured in industry for the production of chemicals that can be used as solvents, glues, anaesthetics, and precursor for plastics. However, the usual industrial conditions applied make use of high pressure and temperature. By focusing attention on the production of commodities like vinyl chloride monomer, and chloroethane we have seen that these kinds of products can be obtained under mild conditions when gold is used as a catalyst, and with high selectivity. Moreover, a tuneable effect can be obtained using different supports, or gold oxidation states. Although gold as a catalyst for the hydrochlorination of acetylene is known, no literature is available on the effect of adding another metal, either as a bimetallic or an alloy system, on final activity. For this reason, the effect of adding metals such as Pd, Pt, Ru, Rh, It has been investigated. Gold alone gives the most stable performance. However, when Au/Pd is used an initial promotional effect is observed. Although this effect is not a long term effect, it has been possible to detect an influence of the gold oxidation state and to identify clearly the gold oxidation state responsible for the hydrochlorination of acetylene and the mechanism of catalyst deactivation. Using carbon as a support, only carbon-carbon triple bonds are reacted and ethylene is unreactive. For this reason selectivity to vinyl chloride monomer in excess of 99% is achieved. This particular behaviour has been explained by postulating the formation of a C2H2/AU/HCI complex, and this hypothesis is supported by the use of deuterated reagents and molecular modelling investigations

What Do Agent-Based and Equation-Based Modelling Tell Us About Social Conventions: The Clash Between ABM and EBM in a Congestion Game Framework

In this work simulation-based and analytical results on the emergence steady states in traffic-like interactions are presented and discussed. The objective of the paper is twofold: i) investigating the role of social conventions in coordination problem situations, and more specifically in congestion games; ii) comparing simulation-based and analytical results to figure out what these methodologies can tell us on the subject matter. Our main issue is that Agent-Based Modelling (ABM) and the Equation-Based Modelling (EBM) are not alternative, but in some circumstances complementary, and suggest some features distinguishing these two ways of modeling that go beyond the practical considerations provided by Parunak H.V.D., Robert Savit and Rick L. Riolo. Our model is based on the interaction of strategies of heterogeneous agents who have to cross a junction. In each junction there are only four inputs, each of which is passable only in the direction of the intersection and can be occupied only by an agent one at a time. The results generated by ABM simulations provide structured data for developing the analytical model through which generalizing the simulation results and make predictions. ABM simulations are artifacts that generate empirical data on the basis of the variables, properties, local rules and critical factors the modeler decides to implement into the model; in this way simulations allow generating controlled data, useful to test the theory and reduce the complexity, while EBM allows to close them, making thus possible to falsify them.Agent-Based Modelling, Equation-Based Modelling, Congestion Game, Model of Social Phenomena