Chemical equilibrium has proven extremely useful for predicting the chemical composition of AGB atmospheres. Here we use a recently developed code and an updated thermochemical database that includes ...gaseous and condensed species involving 34 elements to compute the chemical equilibrium composition of AGB atmospheres of M-, S-, and C-type stars. We include for the first time Ti
C
clusters, with
= 1-4 and
= 1-4, and selected larger clusters ranging up to Ti
C
, for which thermochemical data are obtained from quantum-chemical calculations. Our main aims are to systematically survey the main reservoirs of each element in AGB atmospheres, review the successes and failures of chemical equilibrium by comparing it with the latest observational data, identify potentially detectable molecules that have not yet been observed, and diagnose the most likely gas-phase precursors of dust and determine which clusters might act as building blocks of dust grains. We find that in general, chemical equilibrium reproduces the observed abundances of parent molecules in circumstellar envelopes of AGB stars well. There are, however, severe discrepancies of several orders of magnitude for some parent molecules that are observed to be anomalously overabundant with respect to the predictions of chemical equilibrium. These are HCN, CS, NH
, and SO
in M-type stars, H
O and NH
in S-type stars, and the hydrides H
O, NH
, SiH
, and PH
in C-type stars. Several molecules have not yet been observed in AGB atmospheres but are predicted with non-negligible abundances and are good candidates for detection with observatories such as ALMA. The most interesting ones are SiC
, SiNH, SiCl, PS, HBO, and the metal-containing molecules MgS, CaS, CaOH, CaCl, CaF, ScO, ZrO, VO, FeS, CoH, and NiS. In agreement with previous studies, the first condensates predicted to appear in C-rich atmospheres are found to be carbon, TiC, and SiC, while Al
O
is the first major condensate expected in O-rich outflows. According to our chemical equilibrium calculations, the gas-phase precursors of carbon dust are probably acetylene, atomic carbon, and/or C
, while for silicon carbide dust, the most likely precursors are the molecules SiC
and Si
C. In the case of titanium carbide dust, atomic Ti is the major reservoir of this element in the inner regions of AGB atmospheres, and therefore it is probably the main supplier of titanium during the formation of TiC dust. However, chemical equilibrium predicts that large titanium-carbon clusters such as Ti
C
and Ti
C
become the major reservoirs of titanium at the expense of atomic Ti in the region where condensation of TiC is expected to occur. This suggests that the assembly of large Ti
C
clusters might be related to the formation of the first condensation nuclei of TiC. In the case of Al
O
dust, chemical equilibrium indicates that atomic Al and the carriers of Al-O bonds AlOH, AlO, and Al
O are the most likely gas-phase precursors.
We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactors and the performances of the resulting setup for spectroscopy and chemical ...simulations in laboratory astrophysics. Several experiments including cold plasma generation and UV photochemistry were performed in a 40 cm long gas cell placed in the beam path of the Aries 40 m radio telescope receivers operating in the 41–49 GHz frequency range interfaced with fast Fourier transform spectrometers providing 2 GHz bandwidth and 38 kHz resolution. The impedance matching of the cell windows has been studied using different materials. The choice of the material and its thickness was critical to obtain a sensitivity identical to that of standard radio astronomical observations. Spectroscopic signals arising from very low partial pressures of CH3OH, CH3CH2OH, HCOOH, OCS, CS, SO2 (<10-3 mbar) were detected in a few seconds. Fast data acquisition was achieved allowing for kinetic measurements in fragmentation experiments using electron impact or UV irradiation. Time evolution of chemical reactions involving OCS, O2 and CS2 was also observed demonstrating that reactive species, such as CS, can be maintained with high abundance in the gas phase during these experiments.
Aims. We present the novel InterStellar Astrochemistry Chamber (ISAC), designed for studying solids (ice mantles, organics, and silicates) in interstellar and circumstellar environments: ...characterizing their physico-chemical properties and monitoring their evolution as caused by (i) vacuum-UV irradiation; (ii) cosmic ray irradiation; and (iii) thermal processing. Experimental study of thermal and photodesorption of the CO ice reported here simulates the freeze-out and desorption of CO on grains, providing new information on these processes. Methods. ISAC is an UHV set-up, with base pressure down to P = 2.5 × 10-11 mbar, where an ice layer is deposited at 7 K and can be UV-irradiated. The evolution of the solid sample was monitored by in situ transmittance FTIR spectroscopy, while the volatile species were monitored by QMS. Results. The UHV conditions of ISAC allow experiments under extremely clean conditions. Transmittance FTIR spectroscopy coupled to QMS proved to be ideal for in situ monitoring of ice processes that include radiation and thermal annealing. Thermal desorption of CO starting at 15 K, induced by the release of H2 from the CO ice, was observed. We measured the photodesorption yield of CO ice per incident photon at 7, 8, and 15 K, respectively yielding 6.4 ± 0.5 × 10-2, 5.4 ± 0.5 × 10-2, and 3.5 ± 0.5 × 10-2 CO molecules photon (7.3–10.5 eV)-1. Our value of the photodesorption yield of CO ice at 15 K is about one order of magnitude higher than the previous estimate. We confirmed that the photodesorption yield is constant during irradiation and independent of the ice thickness. Only below ~ 5 monolayers ice thickness the photodesorption rate decreases, which suggests that only the UV photons absorbed in the top 5 monolayers led to photodesorption. The measured CO photodesorption quantum yield at 7 K per absorbed photon in the top 5 monolayers is 3.4 molecules photon-1. Conclusions. Experimental values were used as input for a simple model of a quiescent cloud interior. Photodesorption seems to explain the observations of CO in the gas phase for densities below 3–7 × 104 cm-3. For the same density of a cloud, 3 × 104 cm-3, thermal desorption of CO is not triggered until T = 14.5 K. This has important implications for CO ice mantle build up in dark clouds.
We report hot filament thermal CVD (HFTCVD) as a new hybrid of hot filament and thermal CVD and demonstrate its feasibility by producing high quality large area strictly monolayer graphene films on ...Cu substrates. Gradient in gas composition and flow rate that arises due to smart placement of the substrate inside the Ta filament wound alumina tube accompanied by radical formation on Ta due to precracking coupled with substrate mediated physicochemical processes like diffusion, polymerization etc., led to graphene growth. We further confirmed our mechanistic hypothesis by depositing graphene on Ni and SiO(2)/Si substrates. HFTCVD can be further extended to dope graphene with various heteroatoms (H, N, and B, etc.,), combine with functional materials (diamond, carbon nanotubes etc.,) and can be extended to all other materials (Si, SiO(2), SiC etc.,) and processes (initiator polymerization, TFT processing) possible by HFCVD and thermal CVD.
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•Oxygen intercalation reduces the strong interaction between graphene and metal.•The intercalation process is achieved by thermal annealing in oxygen atmosphere.•Different surface ...techniques confirm the success of the intercalation process.•Raman spectroscopy demonstrates that the intercalation process leads to decoupling.
We investigate the intercalation process of oxygen in-between a PVD-grown graphene layer and different copper substrates as a methodology for reducing the substrate-layer interaction. This growth method leads to an extended defect-free graphene layer that strongly couples with the substrate. We have found, by means of X-ray photoelectron spectroscopy, that after oxygen exposure at different temperatures, ranging from 280 °C to 550 °C, oxygen intercalates at the interface of graphene grown on Cu foil at an optimal temperature of 500 °C. The low energy electron diffraction technique confirms the adsorption of an atomic oxygen adlayer on top of the Cu surface and below graphene after oxygen exposure at elevated temperature, but no oxidation of the substrate is induced. The emergence of the 2D Raman peak, quenched by the large interaction with the substrate, reveals that the intercalation process induces a structural undoing. As suggested by atomic force microscopy, the oxygen intercalation does not change significantly the surface morphology. Moreover, theoretical simulations provide further insights into the electronic and structural undoing process. This protocol opens the door to an efficient methodology to weaken the graphene-substrate interaction for a more efficient transfer to arbitrary surfaces.
During their thermally pulsing phase, asymptotic giant branch (AGB) stars eject material that forms extended dusty envelopes
. Visible polarimetric imaging found clumpy dust clouds within two stellar ...radii of several oxygen-rich stars
. Inhomogeneous molecular gas has also been observed in multiple emission lines within several stellar radii of different oxygen-rich stars, including W Hya and Mira
. At the stellar surface level, infrared images have shown intricate structures around the carbon semiregular variable R Scl and in the S-type star π
Gru
. Infrared images have also shown clumpy dust structures within a few stellar radii of the prototypical carbon AGB star IRC+10°216 (refs.
), and studies of molecular gas distribution beyond the dust formation zone have also shown complex circumstellar structures
. Because of the lack of sufficient spatial resolution, however, the distribution of molecular gas in the stellar atmosphere and the dust formation zone of AGB carbon stars is not known, nor is how it is subsequently expelled. Here we report observations with a resolution of one stellar radius of the recently formed dust and molecular gas in the atmosphere of IRC+10°216. Lines of HCN, SiS and SiC
appear at different radii and in different clumps, which we interpret as large convective cells in the photosphere, as seen in Betelgeuse
. The convective cells coalesce with pulsation, causing anisotropies that, together with companions
, shape its circumstellar envelope.
The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or ...catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu
to CuO through Cu
O, and their mixtures) at different stages in the machine.
Linear carbon chains are common in various types of astronomical molecular sources. Possible formation mechanisms involve both bottom-up and top-down routes. We have carried out a combined ...observational and modeling study of the formation of carbon chains in the C-star envelope IRC +10216, where the polymerization of acetylene and hydrogen cyanide induced by ultraviolet photons can drive the formation of linear carbon chains of increasing length. We have used ALMA to map the emission of λ 3 mm rotational lines of the hydrocarbon radicals C2H, C4H, and C6H, and the CN-containing species CN, C3N, HC3N, and HC5N with an angular resolution of ~1′′. The spatial distribution of all these species is a hollow 5–10′′ wide spherical shell located at a radius of 10–20′′ from the star, with no appreciable emission close to the star. Our observations resolve the broad shell of carbon chains into thinner subshells that are 1–2′′ wide and not fully concentric, indicating that the mass-loss process has been discontinuous and not fully isotropic. The radial distributions of the species mapped reveal subtle differences: while the hydrocarbon radicals have very similar radial distributions, the CN-containing species show more diverse distributions, with HC3N appearing earlier in the expansion and the radical CN extending later than the rest of the species. The observed morphology can be rationalized by a chemical model in which the growth of polyynes is mainly produced by rapid gas-phase chemical reactions of C2H and C4H radicals with unsaturated hydrocarbons, while cyanopolyynes are mainly formed from polyynes in gas-phase reactions with CN and C3N radicals.
We present a new protocol to grow large-area, high-quality single-layer graphene on Cu foils at relatively low temperatures. We use C60 molecules evaporated in ultra high vacuum conditions as carbon ...source. This clean environment results in a strong reduction of oxygen-containing groups as depicted by X-ray photoelectron spectroscopy (XPS). Unzipping of C60 is thermally promoted by annealing the substrate at 800 °C during evaporation. The graphene layer extends over areas larger than the Cu crystallite size, although it is changing its orientation with respect to the surface in the wrinkles and grain boundaries, producing a modulated ring in the low energy electron diffraction (LEED) pattern. This protocol is a self-limiting process leading exclusively to one single graphene layer. Raman spectroscopy confirms the high quality of the grown graphene. This layer exhibits an unperturbed Dirac-cone with a clear n-doping of 0.77 eV, which is caused by the interaction between graphene and substrate. Density functional theory (DFT) calculations show that this interaction can be induced by a coupling between graphene and substrate at specific points of the structure leading to a local sp3 configuration, which also contribute to the D-band in the Raman spectra.
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We present a new experimental set-up devoted to the study of gas phase molecules and processes using broad-band high spectral resolution rotational spectroscopy. A reactor chamber is equipped with ...radio receivers similar to those used by radio astronomers to search for molecular emission in space. The whole range of the Q (31.5–50 GHz) and W bands (72–116.5 GHz) is available for rotational spectroscopy observations. The receivers are equipped with 16 × 2.5 GHz fast Fourier transform spectrometers with a spectral resolution of 38.14 kHz allowing the simultaneous observation of the complete Q band and one-third of the W band. The whole W band can be observed in three settings in which the Q band is always observed. Species such as CH3CN, OCS, and SO2 are detected, together with many of their isotopologues and vibrationally excited states, in very short observing times. The system permits automatic overnight observations, and integration times as long as 2.4 × 105 s have been reached. The chamber is equipped with a radiofrequency source to produce cold plasmas, and with four ultraviolet lamps to study photochemical processes. Plasmas of CH4, N2, CH3CN, NH3, O2, and H2, among other species, have been generated and the molecular products easily identified by the rotational spectrum, and via mass spectrometry and optical spectroscopy. Finally, the rotational spectrum of the lowest energy conformer of CH3CH2NHCHO (N-ethylformamide), a molecule previously characterized in microwave rotational spectroscopy, has been measured up to 116.5 GHz, allowing the accurate determination of its rotational and distortion constants and its search in space.
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