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SummaryIn this work we elaborate on the idea of a formal theory for a limited but important part of structural chemistry, that described by Lewis’ methods and VSEPR (Valence Shell Electron Pair Repulsion). For this purpose, recursive functions and propositional functions are defined, that apply to formal expressions of the structure, based on a finite set of symbols. This approach allows for the expression of numerous questions of chemical interest. The formalization of basic structural chemistry based on Lewis/VSEPR method is potentially useful for the automation of the related procedures, but possibly also of some use as complementary material in teaching and as a heuristic tool in structural chemistry.

In this work, we study the kinetics of thermal decomposition of MgCO3 in the form of particles of known size. In the experiments, the material is heated to a known temperature in a vacuum oven, and it is characterized, both before and after heating, by infrared spectroscopy and gravimetry. The agreement between the results of the two techniques is excellent. These results are rationalized by means of a model based on Languir’s law, and the comparison with the experiments allows us to estimate the activation energy of the process. The reabsorption of atmospheric water by the oxide is shown spectroscopically, finding that is strongly influenced by the temperature of the process.

The biotic scenario of the selection of biological homochirality is one of the most interesting applications of computer modelling to astrobiology. These scenarios have been studied for more than 70 years, yet there are plenty of studies to better assess them, in particular in the development of models of the selective extinction process. In this paper, we review former studies performed by biology-grounded models of this process and present a new class of computer programs: they further demonstrate the complexity of the selective extinction dynamics and the role played into it by non-trivial chemical-physical concepts. Indeed, the results display large and persistent differences between the populations of the two different chiral types, made possible by the freedom of individual populations to fluctuate wildly while the total population is stabilized by the limited availability of chemical energy. Such strong differences ultimately lead to the selective extinction of one of the two types. This way, computer simulations provide increasing evidence in favour of the biotic scenario.

We investigate the potential energy surfaces (PESs) of the hydrogen-based cation H2+ and the neutral molecule H2 confined inside an infinite potential well in the shape of a regular icosahedron. The numerical computations are performed using the diffusion Monte Carlo method and are based on an analytical technique for obtaining simple equations of the surfaces of convex polyhedra proposed by S. Onaka. Different states and different orientations of the molecules inside the confining potential well, as well as various sizes of the latter, are studied. We provide a detailed symmetry analysis and consistent labeling of the H2+ states considered. The results show that the icosahedral confinement is closely isotropic in its inner region, leading to PESs that develop pronounced minima, as in the case of simpler confinement geometries. Shape-specific effects can be evidenced when the nuclei are in contact with the confining wall.

The Fokker-Planck (FP) approach for the description of vibrational kinetics is extended in order to include multiquanta transitions and time dependent solutions. Due to the importance of vibrational ladder climbing for the optimization of plasma-assisted nitrogen fixation, nitrogen is used as a test case with a comprehensive set of elementary processes affecting the vibrational distribution function (VDF). The inclusion of the vibrational energy equation is shown to be the best way to model transient conditions in a plasma reactor using the FP approach. Results are benchmarked against results from the widely employed state-to-state (STS) approach for a wide parameters range. STS and FP solutions agree within ∼10% for the lowest vibrational levels, while time dependent VDFs are in agreement with the STS solution within a ∼ 5% error. Using the FP approach offers the possibility to parametrize drift and diffusion coefficients in energy space as a function of vibrational and gas temperature, providing intuitive and immediate insights into energy transport within the vibrational manifold.

The prevalent presence of a single chiral variant of molecules in live organisms is one of the most distinctive signs of life as a global phenomenon. One of the greatest ambitions of biochemistry and astrobiology is to provide an explanation of this predominance. Several mechanisms were proposed in the past, from the propagation of chirality from a homo-chiral substrate to the amplification of effects associated with electro-weak interactions. Here, a different scenario is proposed: anomalous fluctuations associated with a self-replication scenario can lead to the selective extinction of primordial organisms using one of two enantiomers as an enzyme. These fluctuations arise spontaneously under very general conditions. The idea is based on three key points: (a) the simulation of early biological processes as a ‘board game’; (b) the presence of large fluctuations during an autocatalytic process; (c) the presence of a limited source of chemical energy, inducing a form of competition in a primordial replicator population. In order to demonstrate this mechanism, a computational model is developed, describing the ‘struggle for life’ of two different kinds of primordial replicators on a ‘chessboard’ with periodic boundary conditions; each replicator employs enzymes of different chirality on a non-chiral substrate, thereby with no selective advantage. The replication occurs randomly and with a fixed probability, providing that a sufficient amount of chemical energy is locally available. For the first time, our model includes the local balance of chemical energy in a molecular form on the substrate. The correlation between the chemical energy and the local populations is shown. Results clearly show that strong fluctuations in the number of individuals of each species and subsequent selective extinction events of one of the two species are observed. These studies may contribute to shed light on the most mysterious phase transition that occurred during the biochemical evolution of our planet.

In this work, we study the passage through the Martian atmosphere of micrometeorites with a white soft mineral (WSM) composition, which have been proposed as transporters of organic molecules in the solar system. The atmospheric entry model includes the dynamics of the atmospheric entry and the physico-chemical aspects of the thermal decomposition process. The results show that, due to the reduced entry speed, Mars may have been a promising collector of matter in this form. In particular, the chemical decomposition process is much more effective than in the case of the Earth's atmosphere in maintaining a moderate temperature of the micrometeorite during most of the entry process.

Introduction In the research on the origin of life on our Planet, the possibility of a contribution played by organic substances of extraterrestrial origin, which may have reached our planet through micro-fragments of planetary and cometary origin, is being taken into consideration more and more seriously (Flynn et al., 2003). These particles may also provide the necessary thermal protection for thermolabile, life-related molecules, to the high temperatures reached during the first stages of the atmospheric entry processes. Particularly interesting is the size of the order of a tenth of a millimeter, which corresponds to a peak in the distribution of the material entering the atmosphere. Physical models of the entry process of such grains have been available in the literature for many years. When the composition of most promising mineral phase is considered, the most interesting candidates are carbonates (mostly of Mg, Ca, and Fe) which have been associated, in meteorites and in cometary grains, with organic molecules (McKay et. al., 1996; Flynn et al., 2000; Pizzarello et al., 2006; Matrajt et al., 2012) for several reasons. Carbonates are very common in the Solar System. Outside the Earth, they have been identified on the surface of Mars (Ehlmann et al., 2008; Palomba et al., 2009; Wray et al., 2016), on Ceres (Rivkin et al., 2006; De Sanctis et al., 2016) and tentatively on other asteroids (Rivkin, 2009) as well as in cometary comas (Fomenkova et al., 1992; Lisse et al., 2006; Wirick et al., 2007). Since these astrophysical sites are thought to be the main sources of meteorites and micrometeorites, it is not surprising to find carbonates also in these small objects which reach our planet. In particular, Mg-, Ca-, and Fe/Mn-rich carbonate globules of putative biotic origin have been found in the Martian meteorite ALH84001 (McKay et al., 1996). Carbonate decomposition All the available studies of the atmospheric entry grains assume compositions corresponding to the bulk of meteorite bodies, i.e. silicates and metals. Only recently, carbonates have been taken in account as carriers in an astrobiological perspective (Bisceglia et al., 2017; Micca Longo & Longo, 2017; 2018). Carbonates are known to undergo decomposition in vacuum at temperatures of a few hundred °C (producing metal oxides and gaseous carbon dioxide) (L’vov, 1997; 2002). Therefore, during the atmospheric entry, the grains with carbonate composition are expected to be enriched in oxides and depleted of the initial carbonate amount. This process, being endothermic, can contribute to the thermal protection of associated organic matter. However, the kinetics of the decomposition under such conditions is not well understood. The decomposition model developed in Micca Longo & Longo (2017 and 2018) is based on a well-mixed and ideal solid mixture, and it allows a first evaluation of grains behavior during their passage through the Earth’s atmosphere. The Langmuir law allows to calculate the evaporation rate, per unit time and area, as stated in Bisceglia et al. (2017), in terms of the vapor pressure for the solid mixture carbonate/oxide. Laboratory measurements The kinetics of CO2 diffusion within this kind of grains is still a subject if study. A first attempt was done in Micca Longo et al. (2019) where an important role for the evolution of the model was given to the interpretation of laboratory experiments emulating the conditions during the atmospheric entry processes. In this work, we report the laboratory measurements on Ca and Mg carbonates done to follow the diffusion process of CO2 within such materials. Powders were thermally processed under vacuum (10-4 and 10-5 mbar), for about 3.5 hours, at several temperatures by using a Carbolite furnace able to reach temperatures up to 1200°C. Infrared spectroscopy, gravimetry, Scanning Electron Microscopy, and Energy Dispersive X-ray analysis were involved to investigate spectral, morphological, and compositional modifications induced by thermal processing as done in Orofino et al. (2007), Blanco et al. (2011) and Micca Longo et al. (2019). References Bisceglia E., Micca Longo G., Longo S. (2017) International Journal of Astrobiology 16, 130. Blanco A., et al. (2011) Icarus 213, 473. De Sanctis M.C., et al. (2016) Nature 536, 54. Ehlmann B.L., et al. (2008) Science 322, 1828. Flynn G.J., et al. (2000) Bioastronomy 99, 213. Flynn G.J., et al. (2003) Geochimica et Cosmochimica Acta 67, 4791. Fomenkova M.N., et al. (1992) Science 258, 266. Lisse C.M., et al. (2006) Science 313, 635. L’vov B.V. (1997) Thermochimica Acta 303, 161. L’vov B.V. (2002) Thermochimica Acta 386, 1. Matrajt G., et al. (2012) Meteoritics & Planetary Science 47, 525. McKay D.S., et al. (1996) Science 273, 924–930. Micca Longo G., Longo S. (2017) International Journal of Astrobiology 16, 368. Micca Longo G., Longo S. (2018) Icarus. doi: 10.1016/j.icarus.2017.12.001 Micca Longo G., et al. (2019) Geoscience. doi: 10.3390/geosciences9020101 Orofino V., et al. (2007) Icarus 187, 457. Palomba E., et al. (2009) Icarus 203, 58. Pizzarello S., Cooper G.W., Flynn G.J. (2006) Meteorites & the Early Solar System 2, 625. Rivkin A.S. (2009) Division for Planetary Sciences Meeting Abstracts 41, Abstract #32.07. Wirick S., et al. (2007) Lunar and Planetary Science Conference Proceedings 38, Abstract #1534. Wray J.J., et al. (2016) Journal of Geophysical Research: Planets 121, 652.

We review the recent progress in the modeling of plasmas or ionized gases, with compositions compatible with that of primordial atmospheres. The plasma kinetics involves elementary processes by which free electrons ultimately activate weakly reactive molecules, such as carbon dioxide or methane, thereby potentially starting prebiotic reaction chains. These processes include electron–molecule reactions and energy exchanges between molecules. They are basic processes, for example, in the famous Miller-Urey experiment, and become relevant in any prebiotic scenario where the primordial atmosphere is significantly ionized by electrical activity, photoionization or meteor phenomena. The kinetics of plasma displays remarkable complexity due to the non-equilibrium features of the energy distributions involved. In particular, we argue that two concepts developed by the plasma modeling community, the electron velocity distribution function and the vibrational distribution function, may unlock much new information and provide insight into prebiotic processes initiated by electron–molecule collisions.

This topical review gathers the last updates concerning caesium-free negative ion sources presented during the $$63{\mathrm {rd}}$$ Course of the International school of Quantum Electronics of the Ettore Majorana Foundation and European collaborative works related to these lectures. Hence, beyond the frame of this course this topical review addresses both theoretical and experimental work performed during these last few years and complexities represented by the conception of a negative ion source ranging from the creation of negative ions to their neutralization.

Computer modeling technique based on the theory of stochastic processes have been used in order to provide a realistic simulation of the behavior of nanoscopic systems, related in particular to plasma reactors in microelectronic device production. Basing on decades of experience, we show here, with new results, that the universality of such methods allows the development of codes with the highest reusability and versatility, crossing the barrier of scale. At the smallest scale, the quantum calculations of the potential energy surface of hydrogen species under nano-confinement conditions display the effects due to the dimension and the symmetry of the confining potential well. At a slightly larger scale, nanoparticles dispersed as aerosol in plasma feature strong fluctuations in temperature and charge which may affect the processing of silicon wafers. At the macroscopic scale, using a stochastic solution of transport equations, it is possible to describe laboratory or industrial systems for the production or treatment of nanomaterials, also exploiting the analogy between neutral particle transport and radiative transfer and information obtained by molecular simulations. These findings are relevant in the control of solid-particle contamination in the manufacture of electronic components and in other fields.

Electron velocity distribution functions (EVDFs) in CO2 obtained by means of the Monte Carlo flux (MCF) method are compared with results from two-term and multi-term Boltzmann solvers. The MCF method provides detailed calculations of the EVDF through a highly efficient variance reduction technique. Benchmark calculations of Legendre polynomial coefficients of the EVDF expansion are reported for a wide range of reduced electric fields (E/N), showing excellent agreement with multi-term solutions. Rate coefficients of inelastic processes calculated from two-term Boltzmann solvers differ significantly, up to 70%, from MCF and multi-term solutions, due to the anisotropy of the EVDF. An extension of the method to consider the thermal distribution of the background gas is also presented. This extension, together with an accurate description of the population of rotationally and vibrationally excited states, provides excellent agreement with measured transport coefficients at low E/N. A good agreement is obtained at moderate E/N between experimental values of dissociation rate coefficients and MCF calculations after careful consideration and analysis of several cross sections data sets.

International audience; In this work we investigated different approaches and models used for the estimation of the charge fluctuation of solid particles in dusty plasmas. We compared the charge distributions inferred from these models and analysed the consequences in terms of coagulation kinetics and particle size distributions. We especially showed that taking explicitly into account the discrete nature of the charging process along with the enhancement of ion flux due to ion-neutral elastic collisions result in significantly larger values for the fractions of neutral and positively charged particles, which affects the coagulation kinetics and the predicted values of particle density. We also showed, by comparing sectional and modal approaches, that the typical size-distributions obtained in the studied plasmas may be well described using a bimodal distribution with a single size nucleation mode and a Gaussian large-size mode. Such a possibility enables a great simplification of the aerosol dynamic description and open up an interesting perspective as far as multidimensionnal self consistent modeling of dusty plasmas is concerned.

A model of the atmospheric entry of sub-mm grains is employed to evaluate the effect of the chemical composition of the primordial Earth’s atmosphere on the grain heating, in the context of organic matter delivery. Calculations are performed with spherical, uniform grains of forsterite/fayalite composition as well with the recently proposed white soft mineral (WSM) grains. Different hypotheses on primordial atmosphere composition affect the scale height and the energy transfer. The present work shows that: the total gas budget of the atmosphere is not highly relevant as far as the determination of the heating associated with slowing to subsonic speed is concerned; accordingly, light components (which are expected to be present in a primordial atmosphere and more abundant in the upper one) may be the primary ones in the evaluation of momentum and heat transfer in such scenarios. Strong reduced heating is obtained in the case of an upper atmosphere rich in light components, showing that the composition of the primordial Earth atmosphere may represent the key issue in the delivery of thermolabile organic matter enclosed in sub-mm extraterrestrial grains.

The effect of gas temperature on the transport of the CO2+ ion in its parent gas CO2 is studied. For this purpose, a Monte Carlo (MC) solution technique of the ion transport equation developed in the past by the authors, which was formally proven to provide the exact solution of the transport equation, is used. The study is performed first by benchmarking against experimental data and another MC code, using cross sections from literature and then changing the gas temperature. The solution is characterized through its moments such as reduced mobility, coefficients of its expansion in Legendre polynomials and three-dimensional ion velocity distribution function. It is shown that the gas temperature has a significant effect on all these quantities. This finding has important consequences for plasma modeling which are discussed.

In this work, LIBS (Laser Induced Breakdown Spectroscopy) capability to operate in stand-off configuration, without the need of a direct contact with the sample, has been coupled with the calibration-free (CF) approach to LIBS data analysis. The latter does not require the use of standard calibration. The feasibility of the calibration free method on stand-off LIBS spectra has been thereby tested. The quantitative analysis was performed on samples of two well-known meteorites, Toluca (iron meteorite) and Sahara 98222 (L6 chondrite) by using a stand-off configuration at a distance of 5 m. The plasma temperature and the electron number densities were determined for each sample and for each laser shot in order to apply the CF method. For the Toluca meteorite sample Fe, Ni and Co content was quantified during the depth profile. For the Sahara 98222 major and minor elements (Fe, Mg, Si, Na, Ti, Al, Cr, Mn, Ca, Ni, Co) were analysed by averaging different meteorite zones because of its strong inhomogeneity. Results demonstrate the possibility of remote analysis of minor bodies and space debris.

Current models allow to reliably simulate mechanical and thermal phenomena associated with a micrometeor passage through the Earth’s atmosphere. However, these models have rarely been applied to materials other than those most common in meteorites, such as silicates and metals. A particular case that deserves attention is the one of micrograins made of minerals, in particular carbonates, which have been associated, in meteorites, with organic molecules. Carbonates are known for their decomposition in vacuum at moderate temperatures, and they might contribute to the thermal protection of organic matter. In this work, a model with non isothermal atmosphere, power balance, evaporation, ablation, radiation losses and stoichiometry, is proposed. This paper includes the very first calculations for meteoroids with a mixed carbonate composition. Results show that the carbonate fraction of these objects always go to zero at high altitudes except for grazing entries, where the reached temperature is lower and some carbonate remains unreacted. For all entry conditions, peculiar temperature curves are obtained due to the decomposition process. Furthermore, a significant impact of decomposition cooling on the temperature peak is observed for some grazing entry cases. Although specific solutions used in these calculations can be improved, this work sets a definite model and a basis for future research on sub-mm grains of relatively volatile minerals entering the Earth’s atmosphere.

In this paper, anhydrous calcium sulphate CaSO4(anhydrite) is considered as a carrier material for organic matter delivery from Space to Earth. Its capability of incorporating important fractions of water, leading to different species like bassanite and gypsum, as well as organic molecules; its discovery on Mars surface and in meteorites; the capability to dissipate much energy by its chemical decomposition into solid (CaO) and gaseous (SO3) oxide, make anhydrite a very promising material in an astrobiological perspective. Since chemical cooling has been recently considered by some of the present authors for the case of Ca/Mg carbonates, CaSO4can be placed into a class of ‘white soft minerals’ (WSM) of astrobiological interest. In this context, CaSO4is evaluated here by using the atmospheric entry model previously developed for carbonates. The model includes grain dynamics, thermochemistry, stoichiometry, radiation and evaporation heat losses. Results are discussed in comparison with MgCO3and CaCO3and show that sub-mm anhydrite grains are potentially effective organic matter carriers. A Monte Carlo simulation is used to provide distributions of the sulphate fraction as a function of altitude. Two-zone model results are presented to support the isothermal grain hypothesis.

A rich literature has been produced on the quantum states of atoms and molecules confined into infinite potential wells with a specified symmetry. Apart from their interest as basic quantum systems, confined atoms and molecules are useful models for extreme high-pressure states of matter, spectroscopically active defects in solid lattices, and chemical species in molecular cages. A most important case is that of H $$_2^+$$ for which little or no results are available in the case of polyhedral confinement. The authors’ approach makes use of the Diffusion Monte Carlo (DMC) method. The advantage of this method is that previously developed codes are readily adapted to new, even complex, well geometries, and nuclear positions. In this paper, the potential energy surface (PES) of H $$_2^+$$ confined inside an octahedral well is reported for restricted D $$_{4h}$$ and D $$_{3d}$$ geometries and different well widths. The results are discussed using the concept of electron compression and the correlation with semi-confined atomic orbitals.

In this paper, a first study of the atmospheric entry of carbonate micrometeoroids, in an astrobiological perspective, is performed. Therefore an entry model, which includes two-dimensional dynamics, non-isothermal atmosphere, ablation and radiation losses, is build and benchmarked to literature data for silicate micrometeoroids. A thermal decomposition model of initially pure magnesium carbonate is proposed, and it includes thermal energy, mass loss and the effect of changing composition as the carbonate grain is gradually converted into oxide. Several scenarios are obtained by changing the initial speed, entry angle and grain diameter, producing a systematic comparison of silicate and carbonate grain. The results of the composite model show that the thermal behaviour of magnesium carbonate is markedly different from that of the corresponding silicate, much lower equilibration temperatures being reached in the first stages of the entry. At the same time, the model shows that the limit of a thermal protection scenario, based on magnesium carbonate, is the very high decomposition speed even at moderate temperatures, which results in the total loss of carbon already at about 100 km altitude. The present results show that, although decomposition and associated cooling are important effects in the entry process of carbonate grains, the specific scenario of pure MgCO3micrograin does not allow complex organic matter delivery to the lower atmosphere. This suggests us to consider less volatile carbonates for further studies.

The Fokker-Planck (FP) approach to describe vibrational kinetics numerically is validated in this work. This approach is shown to be around 1000 times faster than the usual state-to-state (STS) method to calculate a vibrational distribution function (VDF) in stationary conditions. Weakly ionized, nonequilibrium CO2 plasma is the test case for this demonstration, in view of its importance for the production of carbon-neutral fuels. VDFs obtained through the resolution of an FP equation and through the usual STS approach are compared in the same conditions, considering the same kinetic data. The demonstration is shown for chemical networks of increasing generality in vibrational kinetics of polyatomic molecules, including V-V exchanges, V-T relaxation, intermode V-V′ reactions, and excitation through e-V collisions. The FP method is shown to be accurate to describe the vibrational kinetics of the CO2 asymmetric stretching mode, while being much faster than the STS approach. In this way, the quantitative validity of the FP approach in vibrational kinetics is assessed, making it a fully viable alternative to STS solvers, that can be used with other processes, molecules, and physical conditions.

The molecular ion H$_2^+$ is studied under strong confinement conditions produced by a spherical barrier centered in the gravity center of the molecule. Results for the potential curves are obtained by diffusion Monte Carlo methods for the ground state (X$^2\Sigma_g^+$) and the first excited state (A$^2\Sigma_u^+$), and reported as functions of the internuclear distance d for different values of the confinement radius. Results show that the compressed state corresponding to both $^2\Sigma_g^+$ and $^2\Sigma_u^+$ present deep minima in their potential curves, due to the increased space for electron wave-functions when the protons are displaced from the barrier surface., Comment: 6 pages, 3 figures, 24 bibliographic references

Modern, multi-modular plasma modeling requires accurate and versatile methods for the determination of the electron velocity distribution function from which rate coefficients of electron impact processes as well as electron transport quantities are determined. In this paper we propose as a solution a modified version of a strongly overlooked method developed in the early 90s, namely, Monte Carlo Flux (MCF). The improvement lies in a criterion for the otherwise somewhat empirical selection of the time-step used in the method. We show that an MCF based code highlights and overcomes the limitations of two-terms codes such as BOLSIG+ and it is much faster than a conventional Monte Carlo. Moreover, MCF is in excellent agreement with the multi-term method for a wide range of reduced electric fields, being at the same time much simpler to implement and to extend to more general cases than the latter. Explicit illustrations of the Markov matrices representing short-time kinetics are presented to gain insight into the method. The two-dimensional velocity distribution and its expansion into Legendre polynomials are discussed for electrons in argon.

In the past few years, a new approach has been experimented for the calculation of the populations of vibrational levels of molecules involved in chemical reactions in ionized gases. The approach that can be defined as neo-diffusive is based on the use of numerical techniques to solve a Fokker–Planck equation in the space of internal energy. The transport coefficients are calculated from the rate coefficients of the reactions between molecules in different vibrational states. It represents a conceptually different alternative to the much used state-to-state (STS) approach, based on the solution of the Master equation. The neo-diffusive approach differs from a similar Fokker–Planck equation-based approach used in the 70s and the 80s of the past century, since exact numerical solutions are used. In this work, the state of the art and perspectives of this new approach are analyzed. Is it pointed out that, while the neo-diffusive method allows us to calculate populations of vibrational levels and reaction rates with much less computational effort than methods based on the Master equation, greatly important is that this method provides a powerful basis for intuition, allowing to highlight effects otherwise obscured by the complex network nature of the STS approach.

International audience; A physically consistent discrete statistical theory for charge and temperature fluctuations is developed which is capable of determining the mean and statistical properties of particle charge and temperature distributions. The statistical parameters obtained using this model are in very good agreement with Monte-Carlo simulations. Results show that the correlation between charge and temperature fluctuations significantly affect the thermal balance for nm-sized particles. We also showed that temperature distribution of nm-sized particles have a significantly populated tail towards high temperatures which may have important consequences on the structure of the particle.

Carbonate minerals, likely of hydrothermal origins and included into orthopyroxenite, have been extensively studied in the ALH84001 meteorite. In this meteorite, nanocrystals comparable with those produced by magnetotactic bacteria have been found into a carbonate matrix. This leads naturally to a discussion of the role of such carbonates in panspermia theories. In this context, the present work sets the basis of a criterion to evaluate whether a carbonate matrix in a meteor entering a planetary atmosphere would be able to reach the surface. As a preliminary step, the composition of carbonate minerals in the ALH84001 meteorite is reviewed; in view of the predominance of Mg in these carbonates, pure magnesite (MgCO3) is proposed as a mineral model. This mineral is much more sensitive to high temperatures reached during an entry process, compared with silicates, due to facile decomposition into MgO and gaseous carbon dioxide (CO2). A most important quantity for further studies is therefore the decomposition rate expressed as CO2evaporation rateJ(molecules/m2s). An analytical expression forJ(T) is given using the Langmuir law, based on CO2pressure in equilibrium with MgCO3and MgO at the surface temperatureT. Results suggest that carbonate minerals rich in magnesium may offer much better thermal protection to embedded biological matter than silicates and significantly better than limestone, which was considered in previous studies, in view of the heat absorbed by their decomposition even at moderate temperatures. This first study can be extended in the future to account for more complex compositions, including Fe and Ca.

Spectral densities of plasma fluctuations are calculated for the thermal case using classical molecular dynamics (MD) assuming Coulomb interactions and a short-range cutoff radius. The aim of the calculation is to verify limits and performances of such calculations in the light of possible generalizations, e.g. collisional or non-ideal plasmas. Results are presented for ideal, collisionless, fully ionized thermal plasmas. Comparison with the analytical theory reveals a generally satisfactory agreement with possibility for improvement when more strict numerical parameters are used albeit with a strong increase in computational cost. The largest deviations have been observed in the vicinity of the weakly damped eigenmodes. The agreement is strong in other parts of the spectrum, where Landau damping is prominent, and overcomes the effects stemming from the excess collisionality and coupling as well as from the exclusion of short-range collisions.

A new approach to calculate the vibrational distribution function of molecules in a medium providing energy for vibrational excitation is proposed and demonstrated. The approach is an improvement of solution methods based on the drift-diffusion Fokker-Planck (FP) equation for a double differentiable function representing the vibrational populations on a continuum internal energy scale. A self-consistent numerical solution avoids approximations used in previous analytical solutions. The dissociation flux, a key parameter in the FP equation, is fixed using the kinetics of molecular dissociation from near-continuum levels, so that the vibrational kinetics becomes a functional problem. The approach is demonstrated for the kinetics of asymmetric stretching of CO2, showing that it represents an alternative, potentially much more efficient in computational terms, to the presently usual state-to-state approach which is based on the kinetics of the populations of individual levels, and gives complementary insight into the dissociation process.

Pulse shape discrimination using CsI(Tl) scintillators to perform neutral hadron particle identification is explored with emphasis towards application at high energy electron-positron collider experiments. Through the analysis of the pulse shape differences between scintillation pulses from photon and hadronic energy deposits using neutron and proton data collected at TRIUMF, it is shown that the pulse shape variations observed for hadrons can be modelled using a third scintillation component for CsI(Tl), in addition to the standard fast and slow components. Techniques for computing the hadronic pulse amplitudes and shape variations are developed and it is shown that the intensity of the additional scintillation component can be computed from the ionization energy loss of the interacting particles. These pulse modelling and simulation methods are integrated with GEANT4 simulation libraries and the predicted pulse shape for CsI(Tl) crystals in a $5 \times 5$ array of $5 \times 5 \times 30 \text{ cm}^3$ crystals is studied for hadronic showers from 0.5 and 1 GeV/c $K_L^0$ and neutron particles. Using a crystal level and cluster level approach for photon vs hadron cluster separation we demonstrate proof-of-concept for neutral hadron detection using CsI(Tl) pulse shape discrimination in high energy electron-positron collider experiments., Comment: This is an author-created, un-copyedited version of an article accepted for publication/published in Journal of Instrumentation. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at https://doi.org/10.1088/1748-0221/13/03/P03018

This contribution proposes a description of selected experimental activities conducted in aerospace sciences and dedicated to generate experimental data to assess atmospheric entry plasma models. In order to provide comprehensive set of experimental data, high enthalpy shock tube facilities have been developed to generate plasma representative of entry plasma for broad range of trajectory entry conditions. The shock-heated plasma is obtained through adiabatic compression and the resulting post-shock plasma flow exhibits thermodynamic state analogous to actual entry plasma. However, significant insight can be obtained through experiments conducted also with non-equilibrium plasma flows obtained with other methods. The typical methodologies adopted to provide experimental data of interest to enhance entry plasma modeling are sketched for four distinct non-equilibrium plasma kinds produced respectively by four specific ground facilities. The contribution firstly will consider experimental campaigns conducted with a high enthalpy shock tube in order to document in absolute radiance the radiative signature in the UV spectral range of an Earth entry plasma. Then, the investigations of the interaction between a shock wave and an electrical discharge will be described. These investigations were performed to identify the role of the internal degrees of freedom of molecular gases on the propagation of the shock. Also, the contribution covers investigations devoted to the thermodynamic state characterizations by means of spectroscopic diagnostics in the cases of the non-equilibrium plasmas flows generated by plasma wind tunnels. The examination of the Saha-Boltzmann equilibrium is proposed in the case of a subsonic plasma flow. And at last, the characterization methods of air supersonic plasma jet are presented and the 2D distributions of the subsequently measured plasma properties are documented for a straight comparisons with non-equilibrium plasma jet computations.

Dissociation of CO2 molecules in plasma is a subject of enormous importance for fundamental studies and in view of the recent interest in carbon capture and carbon-neutral fuels. Vibrational excitation of the CO2 molecule plays an important role in the process. The complexity of the present state-to-state (STS) models makes it difficult to find the key parameters. In this paper we propose, as an alternative, a numerical method based on the diffusion formalism developed in the past for analytical studies. The nonlinear Fokker-Planck equation is solved by the time-dependent diffusion Monte Carlo method. Transport quantities are calculated from STS rate coefficients. The asymmetric stretching mode of CO2 is used as a test case. We show that the method reproduces the STS results or a Treanor distribution depending on the choice of the boundary conditions. A positive drift, whose energy onset is determined by the vibrational to translational temperature ratio, brings molecules from mid-energy range to dissociation. Vibrational-translational energy transfers have negligible effect at the gas temperature considered in this study. The possibility of describing dissociation kinetics as a transport process provides insight toward the goal of achieving efficient CO2 conversion. (Graph Presented).

A comprehensive hybrid model of a hydrogen capacitively coupled plasmas (CCP), including a detailed description of the molecular vibrational kinetics, has been applied to the study of the effect of tailored voltage waveforms (TVWs) on the production kinetics and transport of negative ions in these discharges. Two kinds of TVWs are considered, valleys-to-peaks and saw-tooth, with amplitude and slope asymmetry respectively. By tailoring the voltage waveform only, it is possible to exert substantial control over the peak density and position of negative ions inside the discharge volume. This control is particularly effective for saw-tooth waveforms. Insight into the mechanisms allowing this control is provided by an analysis of the model results. This reveals the roles of the vibrational distribution function and of the electron energy distribution and their correlations, as well as changes in the negative ion transport in the electric field when using different TVWs. Considering the chemical reactivity of H- ions, the possibility of a purely electrical control of the negative ion cloud in a reactor operating with a feedstock gas diluted by hydrogen may find interesting applications. This is the first study of vibrational kinetics in the context of TVWs in molecular gases.

This paper presents an evaluation of Laser Induced Breakdown Spectroscopy (LIBS) as a technique for gathering data relevant to Solar System geophysics. Two test cases were demonstrated: elemental analysis of chondrules in a chondrite meteorite, and space- resolved analysis of the interface between kamacite and taenite crystals in an octahedrite iron meteorite. In particular most major and minor elements (Fe, Mg, Si, Ti, Al, Cr, Mn, Ca, Fe, Ni, Co) in Sahara 98222 (chondrite) and its chondrules, as well as the profile of Ni content in Toluca (iron meteorite), were determined with the Calibration Free (CF) method. A special attention was devoted to exploring the possibilities offered by variants of the basic technique, such as the use of Fe I Boltzmann distribution as an intensity calibration method of the spectroscopic system, and the use of spatially resolved analysis. © 2014 Elsevier B.V. All rights reserved.

Hydrogen economy has been suggested as a possible green alternative to produce energy, also in the framework of transport applications. According to the specific transport means, different kinds of materials can be adopted. The choice of the most suitable materials should then be addressed according to a systematic analysis of available data. In this paper, together with the major physical storage technologies typically used for aerospace applications, additional possible candidates are suggested, namely clathrates hydrates and metal-organic frameworks (MOFs). They are chosen according to the specific features that are asked in the aerospace industry, such as high storage capacities, low weight and materials cost, high cyclability and full reversibility. To this scope, a comprehensive database based on a large set of information from literature (containing, for example, details on the synthesis processes, the operating temperatures and pressures, volumetric and gravimetric capacities) has been created, and specific tools have been developed to query the database. Indeed, the selection of the materials has been performed via an alternative database approach where the queries can be managed using a user-friendly tool, and potential materials can be selected based on any pool of desirable properties in quantitative terms. Essential information and characterization on theoretical and experimental data about these performing materials are provided and commented. As an example, in this paper, the case of clathrates hydrates is shown, and their potential impact is explored and characterized in this context, suggesting the most suitable synthesis processes.

Many mechanisms and related models concerning chiral symmetry breaking in extended reacting and ecological systems have been formulated in the last years. One common feature of most of these proposals is the important role played by autocatalysis and diffusion. In this paper, a classical model of simulated evolution is discussed in terms of chiral symmetry breaking, and the role played by anomalous fluctuations induced by autocatalysis is shown by a simple stochastic approach. The importance of the kinetics of the loss reactions is also discussed.

The production of negative H/D ions in cold plasmas is an important topics for fusion research. The Chapter deals with the mechanisms for the creation of negative ions including dissociative attachment from vibrationally excited H2/D2 molecules as well as from Rydberg states. Models based on the coupling of electron energy distribution function, vibrational kinetics and plasma chemistry in multipole magnetic plasmas are used and their results are validated against sophisticated experiments. Advanced particle models for the transport and extraction of negative ions from high power RF plasmas are then developed for fusion applications.