arXiv subjects

David Gobrecht

Publications and source records attributed to David Gobrecht.

17 recordsLinked to original sources

arXiv2026

Metal Oxide Clusters in Gas Giant Exoplanet Atmospheres

This study investigates the thermal stability and absorption of metal oxide clusters in exoplanetary atmospheres. Utilizing our thermochemical data, we analyze eight distinct cluster families: magnesium oxide (MgO), silicon monoxide (SiO), titanium monoxide (TiO), vanadium monoxide (VO), titanium dioxide (TiO$_2$), vanadium dioxide (VO$_2$), aluminum oxide (Al$_2$O$_3$), and vanadium pentoxide (V$_2$O$_5$). Equilibrium cluster populations as a function of gas temperature and pressure reveal distinct stability regimes. Under solar elemental abundances, (TiO$_2$)$\rm\rm_N$ and (Al$_2$O$_3$)$\rm_N$ are favored at higher temperatures, while (MgO)$\rm_N$ and (SiO)$\rm_N$ dominate at lower temperatures. Computed absorption spectra exhibit strong size- and composition-dependent absorption features in the mid-infrared (8--50~$\mu$m), many of which fall within the wavelength range accessible to \texttt{JWST/MIRI}. We further coupled cluster thermodynamics with 3D general circulation model (GCM) outputs to investigate the cluster stability across the ultra-hot Jupiters (UHJs) WASP-121 b and WASP-18 b, the hot Jupiter (HJ) WASP-39 b, and the warm Jupiter (WJ) WASP-69 b. In WASP-121 b and WASP-18 b, extreme dayside temperatures suppress large-cluster stability, yielding atmospheres dominated by metal ions at low pressures and neutral metals at depth, with limited cluster survival on the nightside and morning terminator. In WASP-39 b, larger clusters are not thermochemically favoured despite the enhanced metallicity; instead, equilibrium chemistry stabilises smaller species, with only TiO showing a tendency toward stable larger cluster forms, likely due to its open d-orbitals. In contrast, WASP-69 b favors the formation of larger metal oxide clusters across an extended pressure range, highlighting WJs as a favorable environment for metal oxide cluster stability.

astro-ph.EP↗

arXiv2025

Condensation sequence of circumstellar cluster seeds (CSCCS)

Traditionally, the condensation sequence of circumstellar dust is predicted based on the thermodynamic stabilities of specific condensates in the macroscopic bulk phase. However, at the (sub-)nanometer scale clusters with non-crystalline structures and significantly different properties are energetically favoured. For this reason, we study the thermodynamic stabilities of metal oxide clusters with generic stoichiometries of M$_2$O$_3$ and M$_3$O$_4$, where M represents a metal atom. With an upper size limit of 50 atoms, we consider clusters with sizes n=1$-$10 for (M$_2$O$_3$)$_n$, and n=1$-$7 for (M$_3$O$_4$)$_n$. The M$_2$O$_3$ clusters comprise alumina (Al$_2$O$_3$), Mg-rich pyroxene (MgSiO$_3$) and a size-limited sample of titanates (CaTiO$_3$), whereas the M$_3$O$_4$ clusters include spinel (MgAl$_2$O$_4$), Mg-rich olivine (Mg$_2$SiO$_4$) and calcium aluminates (CaAl$_2$O$_4$). We find that, apart from the alumina monomer, the aluminum-bearing clusters (Al$_2$O$_3$)$_n$, n=1$-$10, and (MgAl$_2$O$_4$)$_n$, n=1$-$7, are favoured over their silicate counterparts (MgSiO$_3$)$_n$, n=1$-$10 and (Mg$_2$SiO$_4$)$_n$, n=1$-$7. Also, we find that calcium aluminate clusters, CaAl$_2$O$_4$, are energetically more favourable than magnesium aluminate clusters, MgAl$_2$O$_4$. Furthermore, for a limited data set of (CaTiO$_3$)$_n$, n=1$-$2, clusters we find significantly larger stabilities than for the other considered (M$_2$O$_3$)$_n$ clusters, namely Al$_2$O$_3$ and MgSiO$_3$. Future investigations, in particular on titanates and on Ca-rich silicates, are required to draw a more thorough and complete picture of the condensation sequence at the (sub-)nanoscale.

astro-ph.GA↗

arXiv2024

Vanadium oxide clusters in substellar atmospheres: A quantum chemical study

We aim to understand the formation of cloud condensation nuclei in oxygen-rich substellar atmospheres by calculating fundamental properties of the energetically most favorable vanadium oxide molecules and clusters. A hierarchical optimization approach is applied in order to find the most favorable structures for clusters of (VO)$_{N}$ and (VO$_2$)$_{N}$ for N=1-10, and (V$_2$O$_5$)$_{N}$ for N=1-4 and to calculate their thermodynamical potentials. The candidate geometries are initially optimized applying classical interatomic potentials and then refined at the B3LYP/cc-pVTZ level of theory to obtain accurate zero-point energies and thermochemical quantities. We present previously unreported vanadium oxide cluster structures as lowest-energy isomers. We report revised cluster energies and their thermochemical properties. Chemical equilibrium calculations are used to asses the impact of the updated and newly derived thermodynamic potentials on the gas-phase abundances of vanadium-bearing species. In chemical equilibrium, larger clusters from different stoichiometric families are found to be the most abundant vanadium-bearing species for temperatures below ~1000 K, while molecular VO is the most abundant between ~1000 K and ~2000 K. We determine the nucleation rates of each stoichiometric family for a given (T$_{gas}$, p$_{gas}$) profile of a brown dwarf using classical and non-classical nucleation theory. Small differences in the revised Gibbs free energies of the clusters have a large impact on the abundances of vanadium bearing species in chemical equilibrium at temperatures below ~1000 K, which subsequently has an impact on the nucleation rates of each stoichiometric family. We find that with the revised and more accurate cluster data non-classical nucleation rates are up to 15 orders of magnitude higher than classical nucleation rates.

astro-ph.EP↗

arXiv2023

Bottom-up dust nucleation theory in oxygen-rich evolved stars II. Magnesium and calcium aluminate clusters

Spinel (MgAl$_{2}$O$_{4}$) and krotite (CaAl$_{2}$O$_{4}$) are alternative candidates to alumina (Al$_2$O$_3$) as primary dust condensates in the atmospheres of oxygen-rich evolved stars. Moreover, spinel was proposed as a potential carrier of the circumstellar 13 $\mu$m feature. However, the formation of nucleating spinel clusters is challenging; in particular, the inclusion of Mg constitutes a kinetic bottleneck. We aim to understand the initial steps of cosmic dust formation (i.e. nucleation) in oxygen-rich environments using a quantum-chemical bottom-up approach. Starting with an elemental gas-phase composition, we constructed a detailed chemical-kinetic network that describes the formation and destruction of magnesium-, calcium-, and aluminium-bearing molecules as well as the smallest dust-forming (MgAl$_{2}$O$_{4}$)$_1$ and (CaAl$_{2}$O$_{4}$)$_1$ monomer clusters. Different formation scenarios with exothermic pathways were explored, including the alumina (Al$_2$O$_3$) cluster chemistry studied in Paper I of this series. The resulting extensive network was applied to two model stars, a semi-regular variable and a Mira-type star, and to different circumstellar gas trajectories, including a non-pulsating outflow and a pulsating model. We employed global optimisation techniques to find the most favourable (MgAl$_2$O$_4$)$_n$, (CaAl$_2$O$_4$)$_n$, and mixed (Mg$_x$Ca$_{(1-x)}$Al$_2$O$_4$)$_n$ isomers, with $n$=1$-$7 and x$\in$[0..1], and we used high level quantum-chemical methods to determine their potential energies. The growth of larger clusters with $n$=2$-$7 is described by the temperature-dependent Gibbs free energies.In the considered stellar outflow models, spinel clusters do not form in significant amounts. However, we find that in the Mira-type non-pulsating model CaAl$_2$O$_3$(OH)$_2$, a hydroxylated form of the calcium aluminate krotite monomer forms ...

astro-ph.SR↗

arXiv2023

Mechanisms of SiO oxidation: Implications for dust formation

Reactions of SiO molecules have been postulated to initiate efficient formation of silicate dust particles in outflows around dying (AGB) stars. Both OH radicals and H$_2$O molecules can be present in these environments and their reactions with SiO and the smallest SiO cluster, Si$_2$O$_2$, affect the efficiency of eventual dust formation. Rate coefficients of gas-phase oxidation and clustering reactions of SiO, Si$_2$O$_2$ and Si$_2$O$_3$ have been calculated using master equation calculations based on density functional theory calculations. The calculations show that the reactions involving OH are fast. Reactions involving H$_2$O are not efficient routes to oxidation but may under the right conditions lead to hydroxylated species. The reaction of Si$_2$O$_2$ with H$_2$O, which has been suggested as efficient producing Si$_2$O$_3$, is therefore not as efficient as previously thought. If H$_2$O molecules dissociate to form OH radicals, oxidation of SiO and dust formation could be accelerated. Kinetics simulations of oxygen-rich circumstellar environments using our proposed reaction scheme suggest that under typical conditions only small amounts of SiO$_2$ and Si$_2$O$_2$ are formed and that most of the silicon remains as molecular SiO.

astro-ph.GA↗

arXiv2023

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.

astro-ph.EP↗

arXiv2022

Experimental study of the removal of excited state phosphorus atoms by H$_{2}$O and H$_{2}$: implications for the formation of PO in stellar winds

The reactions of the low-lying metastable states of atomic phosphorus, P($^2$D) and P($^2$P), with H$_{2}$O and H$_{2}$ were studied by the pulsed laser photolysis at 248 nm of PCl$_{3}$ , combined with laser induced fluorescence detection of P($^2$D), P($^2$P) and PO. Rate coefficients between 291 and 740 K were measured, along with a yield for the production of PO from P($^2$D or $^2$P) + H$_{2}$O of (35$\pm$15)%. H$_{2}$ reacts with both excited P states relatively efficiently; physical (i.e. collisional) quenching, rather than chemical reaction to produced PH + H, is shown to be the more likely pathway. A comprehensive phosphorus chemistry network is then developed using a combination of electronic structure theory calculations and a Master Equation treatment of reactions taking place over complex potential energy surfaces. The resulting model shows that at the high temperatures within two stellar radii of a MIRA variable AGB star in oxygen-rich conditions, collisional excitation of ground-state P($^4$S) to P($^2$D), followed by reaction with H$_{2}$O, is a significant pathway for producing PO (in addition to the reaction between P($^4$S) and OH). The model also demonstrates that the PN fractional abundance in a steady (non-pulsating) outflow is under-predicted by about 2 orders of magnitude. However, under shocked conditions where sufficient thermal dissociation of N$_2$ occurs at temperatures above 4000 K, the resulting N atoms convert a substantial fraction of PO to PN.

astro-ph.SR↗

arXiv2021

Bottom-up dust nucleation theory in oxygen-rich evolved stars I. Aluminium oxide clusters

Aluminum oxide (alumina, Al$_{2}$O$_{3}$) is a promising candidate as a primary dust condensate in the atmospheres of oxygen-rich evolved stars. Therefore, alumina \textit{seed} particles might trigger the onset of stellar dust formation and of stellar mass loss in the wind. However, the formation of alumina dust grains is not well understood.} {To shed light on the initial steps of cosmic dust formation (i.e. nucleation) in oxygen-rich environments by a quantum-chemical bottom-up approach.} {Starting with an elemental gas-phase composition, we construct a detailed chemical-kinetic network describing the formation and destruction of aluminium-bearing molecules and dust-forming (Al$_{2}$O$_{3}$)$_n$ clusters up to the size of dimers ($n$=2) coagulating to tetramers ($n=$4). Intermediary species include the prevalent gas-phase molecules AlO and AlOH, and Al$_x$O$_y$ clusters with $x=$1$-$5, $y=$1$-$6. The resulting extensive network is applied to two model stars, representing a semi-regular variable and a Mira-type, and to different circumstellar gas trajectories including a non-pulsating outflow and a pulsating model. The growth of larger-sized (Al$_{2}$O$_{3}$)$_n$ clusters with $n=$4$-$10 is described by the temperature-dependent Gibbs free energies of the most favourable structures (i.e. the global minima clusters) as derived from global optimisation techniques and calculated by density functional theory. We provide energies, bond characteristics, electrostatic properties and vibrational spectra of the clusters as a function of size $n$ and compare these to corundum corresponding to the crystalline bulk limit ($n\rightarrow \infty$). {The circumstellar aluminium gas-phase chemistry in oxygen-rich giants is primarily controlled by AlOH and AlO, which are tightly coupled by the reactions AlO+H$_2$, AlO+H$_2$O, and their reverse. Models of ...}

astro-ph.SR↗

arXiv2021

The Ionization Energies of Dust-Forming Metal Oxide Clusters

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 investigated the vertical and adiabatic ionization energies of four different metal-oxide clusters by means of density functional theory. They included clusters of magnesia (MgO)$_n$, silicon monoxide (SiO)$_n$, alumina (Al$_2$O$_3$)$_n$, and titania (TiO$_2$)$_n$ with stoichiometric sizes of $n$=1$-$8. The magnesia, alumina, and titania clusters showed relatively little variation in their ionization energies with respect to the cluster size n: 7.1$-$8.2 eV for (MgO)$_n$, 8.9$-$10.0 eV for (Al$_2$O$_3$)$_n$, and 9.3$-$10.5 eV for (TiO$_2$)$_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 reactions.

astro-ph.GA↗

arXiv2021

The vertical and adiabatic ionization energies of silicon carbide clusters, (SiC)$_n$, with n=1-12

Silicon carbide (SiC) is one of the major cosmic dust components in carbon-rich environments. However, the formation of SiC dust is not well understood. In particular, the initial stages of the SiC condensation (i.e. the SiC nucleation) remain unclear, as the basic building blocks (i.e. molecular clusters) exhibit atomic segregation at the (sub-)nanoscale. We report vertical and adiabatic ionization energies of small silicon carbide clusters, (SiC)$_n$ , n=2-12, ranging from 6.6-10.0 eV, which are lower than for the SiC molecule ($\sim$ 10.6 eV). The most favorable structures of the singly ionized (SiC)$_n^+$, n=5-12, cations resemble their neutral counterparts. However, for sizes n=2-4, these structural analogues are metastable and different cation geometries are favored. Moreover, we find that the (SiC)$_5^+$ cation is likely to be a transition state. Therefore, we place constraints on the stability limit for small, neutral (SiC)$_n$ clusters to persist ionization through (inter)-stellar radiation fields or high temperatures.

astro-ph.GA↗

arXiv2021

Atomium: The astounding complexity of the near circumstellar environment of the M-type AGB star R Hydrae. I. Morpho-kinematical interpretation of CO and SiO emission

Evolved low- to intermediate-mass stars are known to shed their gaseous envelope into a large, dusty, molecule-rich circumstellar nebula which typically develops a high degree of structural complexity. Most of the large-scale, spatially correlated structures in the nebula are thought to originate from the interaction of the stellar wind with a companion. As part of the Atomium large programme, we observed the M-type asymptotic giant branch (AGB) star R Hydrae with ALMA. The morphology of the inner wind of R Hya, which has a known companion at ~3500 au, was determined from maps of CO and SiO obtained at high angular resolution. A map of the CO emission reveals a multi-layered structure consisting of a large elliptical feature at an angular scale of ~10'' that is oriented along the north-south axis. The wind morphology within the elliptical feature is dominated by two hollow bubbles. The bubbles are on opposite sides of the AGB star and lie along an axis with a position angle of ~115 deg. Both bubbles are offset from the central star, and their appearance in the SiO channel maps indicates that they might be shock waves travelling through the AGB wind. An estimate of the dynamical age of the bubbles yields an age of the order of 100 yr, which is in agreement with the previously proposed elapsed time since the star last underwent a thermal pulse. When the CO and SiO emission is examined on subarcsecond angular scales, there is evidence for an inclined, differentially rotating equatorial density enhancement, strongly suggesting the presence of a second nearby companion. The position angle of the major axis of this disc is ~70 deg in the plane of the sky. We tentatively estimate that a lower limit on the mass of the nearby companion is ~0.65 Msol on the basis of the highest measured speeds in the disc and the location of its inner rim at ~6 au from the AGB star.

astro-ph.SR↗

arXiv2020

On the mass and metallicity distribution of parent AGB stars of presolar SiC

The vast majority (>=90%) of presolar SiC grains identified in primitive meteorites are relics of ancient asymptotic giant branch (AGB) stars, whose ejecta were incorporated into the Solar System during its formation. Detailed characterization of these ancient stardust grains has revealed precious information on mixing processes in AGB interiors in great detail. However, the mass and metallicity distribution of their parent stars still remains ambiguous, although such information is crucial to investigating the slow neutron capture process, whose efficiency is mass- and metallicity-dependent. Using a well-known Milky Way chemo-dynamical model, we follow the evolution of the AGB stars that polluted the Solar System at 4.57 Gyr ago and weighted the stars based on their SiC dust productions. We find that presolar SiC in the Solar System predominantly originated from AGB stars with M~2 Msun and Z~Zsun. Our finding well explains the grain-size distribution of presolar SiC identified in situ in primitive meteorites. Moreover, it provides complementary results to very recent papers dealing with the characterization of parent stars of presolar SiC.

astro-ph.SR↗

arXiv2020

Atomium: A high-resolution view on the highly asymmetric wind of the AGB star Pi1 Gruis. I. First detection of a new companion and its effect on the inner wind

The nebular circumstellar environments of cool evolved stars are known to harbour a rich morphological complexity of gaseous structures on different length scales. A large part of these density structures are thought to be brought about by the interaction of the stellar wind with a close companion. The S-type asymptotic giant branch star Pi1 Gruis, which has a known companion at ~440 au and is thought to harbour a second, closer-by (<10 au) companion, was observed with the Atacama Large Millimeter/submillimeter Array as part of the ATOMIUM Large programme. In this work, the brightest CO, SiO, and HCN molecular line transitions are analysed. The continuum map shows two maxima, separated by 0.04'' (6 au). The CO data unambiguously reveal that Pi1 Gru's circumstellar environment harbours an inclined, radially outflowing, equatorial density enhancement. It contains a spiral structure at an angle of 38+/-3 deg with the line-of-sight. The HCN emission in the inner wind reveals a clockwise spiral, with a dynamical crossing time of the spiral arms consistent with a companion at a distance of 0.04'' from the asymptotic giant branch star, which is in agreement with the position of the secondary continuum peak. The inner wind dynamics imply a large acceleration region, consistent with a beta-law power of ~6. The CO emission suggests that the spiral is approximately Archimedean within 5'', beyond which this trend breaks down as the succession of the spiral arms becomes less periodic. The SiO emission at scales smaller than 0.5'' exhibits signatures of gas in rotation, which is found to fit the expected behaviour of gas in the wind-companion interaction zone. An investigation of SiO maser emission reveals what could be a stream of gas accelerating from the surface of the AGB star to the companion. Using these dynamics, we have tentatively derived an upper limit on the companion mass to be ~1.1 Msol.

astro-ph.SR↗

arXiv2019

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.

astro-ph.SR↗

arXiv2018

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] 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.

astro-ph.SR↗

arXiv2018

A global optimisation study of the low-lying isomers of the alumina octomer (Al$_2$O$_3$)$_8$

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 ((Al$_2$O$_3$)$_8$). 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 $T\simeq1300-1450$ K corresponding to a phase transition in liquid alumina.

cond-mat.mtrl-sci↗

arXiv2017

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 $μ$m wavelength range and the 11.3 $μ$m feature inferred from laboratory measurements and observations, respectively, though the overall intensities are rather low.

astro-ph.SR↗