Complementarity between Quantum and Classical Mechanics in Chemical Modeling. The H + HeH+ → H2+ + He Reaction: A Rigourous Test for Reaction Dynamics Methods

In this work we present a dynamical study of the H + HeH+ → H2+ + He reaction in a collision energy range from 0.1 meV to 10 eV, suitable to be used in applicative models. The paper extends and complements a recent work [ Phys. Chem. Chem. Phys. 2014, 16, 11662 ] devoted to the characterization of the reactivity from the ultracold regime up to the three-body dissociation breakup. In particular, the accuracy of the quasi-classical trajectory method below the three-body dissociation threshold has been assessed by a detailed comparison with previous calculations performed with different reaction dynamics methods, whereas the reliability of the results in the high energy range has been checked by a direct comparison with the available experimental data. Integral cross sections for several HeH+ roto-vibrational states have been analyzed and used to understand the extent of quantum effects in the reaction dynamics. By using the quasi-classical trajectory method and quantum mechanical close coupling data, respectively, in the high and low collision energy ranges, we obtain highly accurate thermal rate costants until 15 000 K including all (178) the roto-vibrational bound and quasi-bound states of HeH+. The role of the collision-induced dissociation is also discussed and explicitly calculated for the ground roto-vibrational state of HeH+

A twin-bed test reactor for characterization of calcium looping sorbents

The reduction of sorbent CO2 capture capacity and the extent of particle attrition over iterated cycles are relevant to design of Calcium Looping processes (1-2). Thermogravimetric analyzers or fluidized bed reactors are generally used to evaluate the sorbent performance. One drawback of these reactors is that they do not reproduce the thermal history that is actually experienced by sorbent particles in real looping cycles. In this study, a novel experimental technique is proposed to overcome this limitation. The apparatus consists of two interconnected fluidized bed reactors operating as calciner and carbonator, respectively (Fig. 1). The two reactors are connected each other by a duct (whose openings can be located at adjustable level above the gas distributor) which permits pneumatic transport of the solids between the reactors. Silica sand is used as buffering inert material to prevent excessive temperature fluctuations due to solid transport and chemical reactions. The operating conditions (fluidization velocity and duct height) of the reactor have been tuned to maximize transfer of the sorbent at each cycle, while limiting the transport of sand (Fig. 2). Further tests were carried out to simulate multiple calcination/carbonation cycles (Fig. 3). Under the optimal experimental conditions more than 95% collection efficiency of the limestone was obtained while less than half of the sand was transferred. Additional tests were carried out at high temperature but under non-reacting conditions, so as to simulate the real thermal history of the particles. Please click Additional Files below to see the full abstract

Effect of steam on the performance of Ca-based sorbents in calcium looping processes

Calcium looping, a post-combustion “carbon capture and storage” process (see Figure 1), is usually carried out by means of a limestone-based sorbent in a dual interconnected fluidized bed reactor. The two stages of this process are limestone calcination and carbonation: in the former case, water vapor can be present as a product of the auxiliary fuel combustion needed to drive this endothermal step; in the latter case, water vapor is usually present in the combustion flue gas stream bearing the CO2 to be captured. This work pursues previous research concerning the hydration-induced reactivation of spent sorbents (1,2,3) further and aims at investigating the effect of the presence of water vapor on the performance of a limestone-based sorbent, with particular reference to the attrition/fragmentation tendency. To this end, experimental tests were carried out in a lab-scale apparatus, under typical operating conditions in terms of temperature and gas composition. The role of water vapor in changing the sorbent CO2 capture capacity (with respect to a base-case operation in which water vapor was absent) and the attrition/fragmentation tendency was examined (see, for example, Figure 2 up and down, respectively). Results from CO2 capture will be complemented with characterization of sorbent particles, by means of scanning electron microscopy, porosimetric and X-ray diffraction analyses. Please click Additional Files below to see the full abstract

The Carina Project. VI. The helium burning variable stars

We present new optical (BVI) time-series data for the evolved variable stars in the Carina dwarf spheroidal galaxy. The quality of the data and the observing strategy allowed us to identify 14 new variable stars. Eight out of the 14 are RR Lyrae (RRL) stars, four are Anomalous Cepheids (ACs) and two are geometrical variables. Comparison of the period distribution for the entire sample of RRLs with similar distributions in nearby dSphs and in the Large Magellanic Cloud indicates that the old stellar populations in these systems share similar properties. This finding is also supported by the RRL distribution in the Bailey diagram. On the other hand, the period distribution and the Bailey diagram of ACs display significant differences among the above stellar systems. This evidence suggests that the properties of intermediate-age stellar populations might be affected both by environmental effects and structural parameters. We use the BV Period--Wesenheit (PW) relation of RRLs together with evolutionary prescriptions and find a true distance modulus of 20.09+/-0.07(intrinsic)+/-0.1(statistical) mag that agrees quite well with similar estimates available in the literature. We identified four peculiar variables. Taking into account their position in the Bailey diagram and in the BV PW relation, two of them (V14, V149) appear to be candidate ACs, while two (V158, V182) might be peculiar RRLs. In particular, the variable V158 has a period and a V-band amplitude very similar to the low-mass RRL ---RRLR-02792---recently identified by Pietrzynski at al. (2012) in the Galactic bulge.Comment: Accepted for publication in ApJ, publication date September 20, 2013. 31 pages, 7 figure, 3 tables. Figs. 3 and 4 corrected, references added, minor correction

The Carina Project. X. On the kinematics of old and intermediate-age stellar populations

We present new radial velocity (RV) measurements of old (horizontal branch) and intermediate-age (red clump) stellar tracers in the Carina dwarf spheroidal. They are based on more than 2,200 low-resolution spectra collected with VIMOS at VLT. The targets are faint (20<V<21.5 mag), but the accuracy at the faintest limit is <9 kms-1. These data were complemented with RV measurements either based on spectra collected with FORS2 and FLAMES/GIRAFFE at VLT or available in the literature. We ended up with a sample of 2748 stars and among them 1389 are candidate Carina stars. We found that the intermediate-age stellar component shows a well defined rotational pattern around the minor axis. The western and the eastern side of the galaxy differ by +5 and -4 km s-1 when compared with the main RV peak. The old stellar component is characterized by a larger RV dispersion and does not show evidence of RV pattern. We compared the observed RV distribution with N-body simulations for a former disky dwarf galaxy orbiting a giant MilkyWay-like galaxy (Lokas et al. 2015). We rotated the simulated galaxy by 60 degrees with respect to the major axis, we kept the observer on orbital plane of the dwarf and extracted a sample of stars similar to the observed one. Observed and predicted Vrot/{\sigma} ratios across the central regions are in remarkable agreement. This evidence indicates that Carina was a disky dwarf galaxy that experienced several strong tidal interactions with the Milky Way. Owing to these interactions, Carina transformed from a disky to a prolate spheroid and the rotational velocity transformed into random motions.Comment: 21 pages, 16 figures, 4 tables. Accepted for publication in Ap

The Carina Project IX: on Hydrogen and helium burning variables

We present new multi-band (UBVI) time-series data of helium burning variables in the Carina dwarf spheroidal galaxy. The current sample includes 92 RR Lyrae-six of them are new identifications-and 20 Anomalous Cepheids, one of which is new identification. The analysis of the Bailey diagram shows that the luminosity amplitude of the first overtone component in double-mode variables is located along the long-period tail of regular first overtone variables, while the fundamental component is located along the short-period tale of regular fundamental variables. This evidence further supports the transitional nature of these objects. Moreover, the distribution of Carina double-mode variables in the Petersen diagram (P_1/P_0 vs P_0) is similar to metal-poor globulars (M15, M68), to the dwarf spheroidal Draco and to the Galactic Halo. This suggests that the Carina old stellar population is metal-poor and affected by a small spread in metallicity. We use trigonometric parallaxes for five field RR Lyrae stars to provide an independent estimate of the Carina distance using the observed reddening free Period--Wesenheit [PW, (BV)] relation. Theory and observations indicate that this diagnostic is independent of metallicity. We found a true distance modulus of \mu=20.01\pm0.02 (standard error of the mean) \pm0.05 (standard deviation) mag. We also provided independent estimates of the Carina true distance modulus using four predicted PW relations (BV, BI, VI, BVI) and we found: \mu=(20.08\pm0.007\pm0.07) mag, \mu=(20.06\pm0.006\pm0.06) mag, \mu=(20.07\pm0.008\pm0.08) mag and \mu=(20.06\pm0.006\pm0.06) mag. Finally, we identified more than 100 new SX Phoenicis stars that together with those already known in the literature (340) make Carina a fundamental laboratory to constrain the evolutionary and pulsation properties of these transitional variables.Comment: 44 pages, 13 tables, 13 figures, Accepted for publication in Ap

Canonical Correlation Analysis to Biomass CHONS Prediction

Fermentation biomasses can be defined as a complex mixture of different natural components and microbes, having biodegradable and organic waste as the primary source. Its correct characterization is crucial to have proper processing in fermentative units. Firstly, proximate analysis is done to retrieve the content of specific compounds in the mixture, such as fat, proteins, and carbohydrates. However, this is often not enough to achieve the sufficient precision, since some low-concentration species are not easily found through this methodology (i.e., sulfate compounds, ethanol, caproic acid). Consequently, ultimate analysis is performed to evaluate the exact amount of every element in the mixture. For biomass-based compounds, atoms content can be synthesized in carbon, hydrogen, oxygen, nitrogen, and sulfur. The total content of these elements is also known as CHONS. From this, it is possible to derive the exact amount of the relative species in the biomass. However, the experimental procedure for its determination is rather time and budget-consuming. On the other hand, the amount of data collected in the literature, from both experimental and industrial analysis, can be exploited to build a numerical model, based on the multivariate statistical analysis and machine learning principles that predict the CHONS content for every type of biomass. In this work, a data-driven model has been developed to achieve this aim, having as input a set of relevant variables. Consequently, a dataset has been built to gather all these data. The multivariate statistical technique of Canonical Correlation Analysis (CCA) is used to find 'hidden' correlations and predict CHON content for 27 different biomass types. In future research, machine learning techniques will be applied to compare the results obtained

The Carina Project. VIII. The {\alpha}-element abundances

We have performed a new abundance analysis of Carina Red Giant (RG) stars from spectroscopic data collected with UVES (high resolution) and FLAMES/GIRAFFE (high and medium resolution) at ESO/VLT. The former sample includes 44 RGs, while the latter consists of 65 (high) and ~800 (medium resolution) RGs, covering a significant fraction of the galaxy's RG branch (RGB), and red clump stars. To improve the abundance analysis at the faint magnitude limit, the FLAMES/GIRAFFE data were divided into ten surface gravity and effective temperature bins. The spectra of the stars belonging to the same gravity/temperature bin were stacked. This approach allowed us to increase by at least a factor of five the signal-to-noise ratio in the faint limit (V>20.5mag). We took advantage of the new photometry index cU,B,I introduced by Monelli et al. (2014), as an age and probably a metallicity indicator, to split stars along the RGB. These two stellar populations display distinct [Fe/H] and [Mg/H] distributions: their mean Fe abundances are -2.15$\pm$0.06dex (sig=0.28), and -1.75$\pm$0.03dex (sig=0.21), respectively. The two iron distributions differ at the 75% level. This supports preliminary results by Lemasle et al. (2012) and by Monelli et al. (2014). Moreover, we found that the old and intermediate-age stellar populations have mean [Mg/H] abundances of -1.91$\pm$0.05dex (sig=0.22) and -1.35$\pm$0.03dex (sig=0.22); these differ at the 83% level. Carina's {\alpha}-element abundances agree, within 1sigma, with similar abundances for field Halo stars and for cluster (Galactic, Magellanic) stars. The same outcome applies to nearby dwarf spheroidals and ultra-faint dwarf galaxies, in the iron range covered by Carina stars. Finally, we found evidence of a clear correlation between Na and O abundances, thus suggesting that Carina's chemical enrichment history is quite different than in the globular clusters.Comment: 21 pages, 19 figures, 11 tables, accepted for publication in A&