Nucleation of small silicon carbide dust clusters in AGB stars

Silicon carbide (SiC) grains are a major dust component in carbon-rich AGB stars. The formation pathways of these grains are, however, not fully understood.\ We calculate ground states and energetically low-lying structures of (SiC)$_n$, $n=1,16$ clusters by means of simulated annealing (SA) and Monte Carlo simulations of seed structures and subsequent quantum-mechanical calculations on the density functional level of theory. We derive the infrared (IR) spectra of these clusters and compare the IR signatures to observational and laboratory data.\ According to energetic considerations, we evaluate the viability of SiC cluster growth at several densities and temperatures, characterising various locations and evolutionary states in circumstellar envelopes.\ We discover new, energetically low-lying structures for Si$_{4}$C$_{4}$, Si$_{5}$C$_{5}$, Si$_{15}$C$_{15}$ and Si$_{16}$C$_{16}$, and new ground states for Si$_{10}$C$_{10}$ and Si$_{15}$C$_{15}$. The clusters with carbon-segregated substructures tend to be more stable by 4-9 eV than their bulk-like isomers with alternating Si-C bonds. However, we find ground states with cage ("bucky"-like) geometries for Si$_{12}$C$_{12}$ and Si$_{16}$C$_{16}$ and low-lying, stable cage structures for n $\ge$ 12. The latter findings indicate thus a regime of clusters sizes that differs from small clusters as well as from large-scale crystals. Thus, and owing to their stability and geometry, the latter clusters may mark a transition from a quantum-confined cluster regime to crystalline, solid bulk-material. The calculated vibrational IR spectra of the ground-state SiC clusters shows significant emission. They include the 10-13 $\mu$m wavelength range and the 11.3 $\mu$m feature inferred from laboratory measurements and observations, respectively, though the overall intensities are rather low.Comment: 16 pages, 25 figures, 3 tables, accepted for publication in Ap

Interplay between pulsation, mass loss, and third dredge-up: More about Miras with and without technetium

We follow-up on a previous finding that AGB Mira variables containing the 3DUP indicator technetium (Tc) in their atmosphere form a different sequence of K-[22] colour as a function of pulsation period than Miras without Tc. A near- to mid-infrared colour such as K-[22] is a good probe for the dust mass-loss rate of the stars. Contrary to what might be expected, Tc-poor Miras show redder K-[22] colours (i.e. higher dust mass-loss rates) than Tc-rich Miras at a given period. Here, the previous sample is extended and the analysis is expanded towards other colours and dust spectra. The most important aim is to investigate if the same two sequences can be revealed in the gas mass-loss rate. We analysed new optical spectra and expanded the sample by including more stars from the literature. Near- and mid-IR photometry and ISO dust spectra of our stars were investigated. Literature data of gas mass-loss rates of Miras and semi-regular variables were collected and analysed. Our results show that Tc-poor Miras are redder than Tc-rich Miras in a broad range of the mid-IR, suggesting that the previous finding based on the K-[22] colour is not due to a specific dust feature in the 22 micron band. We establish a linear relation between K-[22] and the gas mass-loss rate. We also find that the 13 micron feature disappears above K-[22]~2.17 mag, corresponding to \dot{M}_{\rm g}\sim2.6\times10^{-7}M_{\sun}yr^{-1}. No similar sequences of Tc-poor and Tc-rich Miras in the gas mass-loss rate vs. period diagram are found, most probably owing to limitations in the available data. Different hypotheses to explain the observation of two sequences in the P vs. K-[22] explain the observation of two sequences in the P vs. K-[22 diagram are discussed and tested, but so far none of them convincingly explains the observations. Nevertheless, we might have found an hitherto unknown but potentially important process influencing mass loss on the TP-AGB.Comment: 16 pages, 15 figures, 2 online tables, accepted for publication in A&

Molecule and dust synthesis in the inner winds of oxygen-rich AGB stars

This thesis aims to explain the masses and compositions of prevalent molecules, dust clusters, and dust grains in the inner winds of oxygen-rich AGB stars. In this context, models have been developed, which account for various stellar conditions, reflecting all the evolutionary stages of AGB stars, as well as different metallicities. Moreover, we aim to gain insight on the nature of dust grains, synthesised by inorganic and metallic clusters with associated structures, energetics, reaction mechanisms, and finally possible formation routes. We model the circumstellar envelopes of AGB stars, covering several C/O ratios below unity and pulsation periods of 100 - 500 days, by employing a chemical-kinetic approach. Periodic shocks, induced by pulsation, with speeds of 10 - 32 km/s enable a non-equilibrium chemistry to take place between 1 and 10 R* above the photosphere. The various models include the well-studied, galactic Mira variables like IK Tau and TX Cam, galactic S-stars, semi-regular variables of type SRa and SRb, as well as Mira stars of lower metallicity in the Magellanic clouds. In addition, we perform quantum-chemical calculations on the Density Functional Theory (DFT) level for several alumina and silicate clusters, in order to obtain structures, electronic properties, and infrared (IR) spectra of the potential dust components. The results for the gas phase agree well with the most recent observational data for IK Tau and VY CMa. Major parent molecules form in the shocked gas under non-equilibrium conditions and include CO, H2O, SiO, SiS, SO and SO2, as well as the unexpected carbon-bearing species HCN, CS and CO2, and the recently detected phosphorous species PO and PN. In the galactic models, small alumina clusters form and condense efficiently close to the star. In the case of galactic Miras, silicate clusters with forsterite mineralogy form and coalesce around 4 R*. In the lower metallicity and semi-regular models, the dust formation is hampered by the unavailability of the critical elements (Si and Al), low densities, and high temperatures. The dust/gas mass ratio ranges from 10^(-9) to 10^(-5) for alumina, and from 10^(-6) to 10^(-3) for forsterite, and agrees with the dust-to-gas mass ratio derived for oxygen-rich AGB stars. For the first time, a complete non-equilibrium model - including gas phase chemistry, cluster growth and dust formation - is built up self-consistently, and explaining successfully the most recent observations

The effect of thermal non-equilibrium on kinetic nucleation

Nucleation is considered to be the first step in dust and cloud formation in the atmospheres of asymptotic giant branch (AGB) stars, exoplanets, and brown dwarfs. In these environments dust and cloud particles grow to macroscopic sizes when gas phase species condense onto cloud condensation nuclei (CCNs). Understanding the formation processes of CCNs and dust in AGB stars is important because the species that formed in their outflows enrich the interstellar medium. Although widely used, the validity of chemical and thermal equilibrium conditions is debatable in some of these highly dynamical astrophysical environments. We aim to derive a kinetic nucleation model that includes the effects of thermal non-equilibrium by adopting different temperatures for nucleating species, and to quantify the impact of thermal non-equilibrium on kinetic nucleation. Forward and backward rate coefficients are derived as part of a collisional kinetic nucleation theory ansatz. The endothermic backward rates are derived from the law of mass action in thermal non-equilibrium. We consider elastic collisions as thermal equilibrium drivers. For homogeneous TiO2 nucleation and a gas temperature of 1250 K, we find that differences in the kinetic cluster temperatures as small as 20 K increase the formation of larger TiO2 clusters by over an order of magnitude. An increase in cluster temperature of around 20 K at gas temperatures of 1000 K can reduce the formation of a larger TiO2 cluster by over an order of magnitude. Our results confirm and quantify the prediction of previous thermal non-equilibrium studies. Small thermal non-equilibria can cause a significant change in the synthesis of larger clusters. Therefore, it is important to use kinetic nucleation models that include thermal non-equilibrium to describe the formation of clusters in environments where even small thermal non-equilibria can be present.Comment: 13 pages, 4 figure

The ionization energies of dust-forming metal oxide clusters

Funding:D.G. and L.D. acknowledge funding by the ERC consolidator grant number 646758. J.-P. S. and H. L.-M. acknowledge the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 860470.Stellar dust grains are predominantly composed of mineralic, anorganic material forming in the circumstellar envelopes of oxygen-rich AGB stars. However, the initial stage of the dust synthesis, or its nucleation, is not well understood. In particular, the chemical nature of the nucleating species, represented by molecular clusters, is uncertain. We investigate the vertical and adiabatic ionization energies of four different metal-oxide clusters by means of density functional theory. They include clusters of magnesia (MgO)n, silicon monoxide (SiO)n, alumina (Al2O3)n, and titania (TiO2)n with stoichiometric sizes of n=1−8. The magnesia, alumina and titania clusters show relatively little variation in their ionization energies with respect to the cluster size n, ranging from 7.1−8.2 eV for (MgO)n, 8.9−10.0 eV for (Al2O3)n, and 9.3−10.5 eV for (TiO2)n. In contrast, the (SiO)n ionization energies decrease with size n, starting from 11.5 eV for n=1, and decreasing to 6.6 eV for n=8. Therefore, we set constraints on the stability limit for neutral metal-oxide clusters to persist ionization through radiation or high temperatures and for the nucleation to proceed via neutral-neutral reactionsPublisher PDFPeer reviewe

Nucleation of small silicon carbide dust clusters in AGB stars

Silicon carbide (SiC) grains are a major dust component in carbon-rich asymptotic giant branch stars. However, the formation pathways of these grains are not fully understood. We calculate ground states and energetically low-lying structures of (SiC)(n), n = 1, 16 clusters by means of simulated annealing and Monte Carlo simulations of seed structures and subsequent quantum-mechanical calculations on the density functional level of theory. We derive the infrared (IR) spectra of these clusters and compare the IR signatures to observational and laboratory data. According to energetic considerations, we evaluate the viability of SiC cluster growth at several densities and temperatures, characterizing various locations and evolutionary states in circumstellar envelopes. We discover new, energetically low-lying structures for Si4C4, Si5C5, Si15C15, and Si16C16 and new ground states for Si10C10 and Si15C15. The clusters with carbon-segregated substructures tend to be more stable by 4-9 eV than their bulk-like isomers with alternating Si-C bonds. However, we find ground states with cage geometries resembling buckminsterfullerens ('bucky-like') for Si12C12 and Si16C16 and low-lying stable cage structures for n >= 12. The latter findings thus indicate a regime of cluster sizes that differ from small clusters as well as from large-scale crystals. Thus-and owing to their stability and geometry-the latter clusters may mark a transition from a quantum-confined cluster regime to a crystalline, solid bulk-material. The calculated vibrational IR spectra of the ground-state SiC clusters show significant emission. They include the 10-13 mu m wavelength range and the 11.3 mu m feature inferred from laboratory measurements and observations, respectively, although the overall intensities are rather low

A global optimisation study of the low-lying isomers of the alumina octomer (Al2O3)8

We employ the Monte-Carlo Basin-Hopping (MC-BH) global optimisation technique with inter- atomic pair potentials to generate low-energy candidates of stoichiometric alumina octomers ((Al2O3)8). The candidate structures are subsequently refined with density functional theory calculations employing hybrid functionals (B3LYP and PBE0) and a large basis set (6-311+G(d)) including a vibrational analysis. We report the discovery of a set of energetically low-lying alumina octomer clusters, including a new global minimum candidate, with shapes that are elongated rather than spherical. We find a stability limit for these and smaller-sized clusters at a temperature of T ≃ 1300 - 1450 K corresponding to a phase transition in liquid alumina

Surface micromachining of UV transparent materials

Abstract A method which utilizes XeCl excimer laser and an absorbing liquid in contact with the material for precise structuring of UV transparent materials is presented. This one step micromachining process enables the fabrication of micro-optical elements with continuous profiles such as Fresnel micro-lenses in CaF and quartz with fluences well below the damage threshold of these 2 materials. The roughness of the etched features varies from 10 nm to 3 mm depending on the laser fluence and material. The etch rates of different UV transparent materials (such as CaF , BaF , sapphire and quartz) at various laser fluences suggest that 2 2 several different parameters influence the etching process.

Agb stars and their circumstellar envelopes. I. the vulcan code

The interplay between AGB interiors and their outermost layers, where molecules and dust form, is a problem of high complexity. As a consequence, physical processes like mass loss, which depend on the chemistry of the circumstellar envelope, are often oversimplified. The best candidates to drive mass-loss in AGB stars are dust grains, which trap the outgoing radiation and drag the surrounding gas. Grains build up, however, is far from being completely understood. Our aim is to model both the physics and the chemistry of the cool expanding layers around AGB stars in order to characterize the on-going chemistry, from atoms to dust grains. This has been our rationale to develop ab initio VULCAN, a FORTRAN hydro code able to follow the propagation of shocks in the circumstellar envelopes of AGB stars. The version presented in this paper adopts a perfect gas law and a very simplified treatment of the radiative transfer effects and dust nucleation. In this paper, we present preliminary results obtained with our code

Developing a self-consistent AGB wind model: II. Non-classical, non-equilibrium polymer nucleation in a chemical mixture

Unravelling the composition and characteristics of gas and dust lost by asymptotic giant branch (AGB) stars is important as these stars play a vital role in the chemical life cycle of galaxies. The general hypothesis of their mass loss mechanism is a combination of stellar pulsations and radiative pressure on dust grains. However, current models simplify dust formation, which starts as a microscopic phase transition called nucleation. Various nucleation theories exist, yet all assume chemical equilibrium, growth restricted by monomers, and commonly use macroscopic properties for a microscopic process. Such simplifications for initial dust formation can have large repercussions on the type, amount, and formation time of dust. By abandoning equilibrium assumptions, discarding growth restrictions, and using quantum mechanical properties, we have constructed and investigated an improved nucleation theory in AGB wind conditions for four dust candidates, TiO$_2$, MgO, SiO and Al$_2$O$_3$. This paper reports the viability of these candidates as first dust precursors and reveals implications of simplified nucleation theories. Monomer restricted growth underpredicts large clusters at low temperatures and overpredicts formation times. Assuming the candidates are present, Al$_2$O$_3$ is the favoured precursor due to its rapid growth at the highest considered temperatures. However, when considering an initially atomic chemical mixture, only TiO$_2$-clusters form. Still, we believe Al$_2$O$_3$ to be the prime candidate due to substantial physical evidence in presolar grains, observations of dust around AGB stars at high temperatures, and its ability to form at high temperatures and expect the missing link to be insufficient quantitative data of Al-reactions.Comment: Accepted for publication in MNRAS. 19 pages (68 incl. appendix