A Possible Additional Formation Pathway for the Interstellar Diatomic SiS

Mendoza E., Costa S.F., Carvajal M., Pilling S., Alves M.O., Galvão B.R.

Context. Among the silicon-bearing species discovered in the interstellar medium, SiS and SiO stand out as key tracers due to their distinct chemistry and variable abundances in interstellar and circumstellar environments. Nevertheless, while the origins of SiO are well documented, the SiS chemistry remains relatively unexplored. Aims. Our objective is to enhance the network of Si- and S-bearing chemical reactions for a gas-grain model in molecular clouds, encompassing both low and high metallicities. To achieve this, we calculated the energies and rate coefficients for six neutral atom-diatom reactions involved in the SiCS triatomic system, with a special focus on the C+SiS and S+SiC collisions. Methods. We employed the coupled-cluster method with single and double substitutions and a perturbative treatment of triple substitutions (CCSD(T)) refined at the explicitly correlated CCSD(T)-F12 level. With these computational results in conjunction with supplementary data from the literature, we construct an extended network of neutral-neutral chemical reactions involving Si- and S-bearing molecules. To assess the impact of these chemical reactions, we performed time-dependent models employing the Nautilus gas-grain code, setting the gas temperature to 10 K and the H2 density to 2 × 104 cm−3. The models considered two initial abundance scenarios, corresponding to low- and high-metallicity levels. Abundances were computed using both the default chemical network and the constrained network, enriched with newly calculated reactions. Results. The temperature dependence for the reactions involving SiS were modelled to the k(T) = α (T/300)β exp (−γ/T) expression, and the coefficients are provided for the first time. The high-metallicity models significantly boost the SiS production, resulting in abundances nearly four orders of magnitude higher compared to low-metallicity models. Higher initial abundances of C, S, and Si, roughly ~2, 190, and 210 times higher, respectively, contribute to this. Around the age of 103 yr, destruction mechanisms become relevant, impacting the abundance of SiS. The proposed production reaction S + SiC → C + SiS, mitigates these effects in later stages. By expanding the gas reaction network using a high-metallicity model, we derived estimates for the abundances of observed interstellar molecules, including SiO, SO, and SO2. Conclusions. We demonstrate the significance of both SiC+S and C+SiS channels in the SiS chemistry. Notably, the inclusion of neutral-neutral mechanisms, particularly via Si+HS and S+SiC channels, played a pivotal role in determining SiS abundance. These mechanisms carry a significance level on a par with that of the well-known and fast ion-neutral reactions.

Firth R.A., Bell K.M., Fortenberry R.C.

Fortenberry R.C.

Palmer C.Z., Fortenberry R.C.

Abstract A dust nucleating agent may be present in interstellar or circumstellar media that has gone seemingly undetected and unstudied for decades. Some analyses of the Murchison CM2 meteorite suggest that at least some of the aluminum present within condensed as aluminum nitrides instead of the long-studied, but heretofore undetected suite of aluminum oxides. The present theoretical study utilizes explicitly correlated coupled cluster theory and density functional theory to provide a formation pathway from alane (AlH3) and ammonia to the cyclic structure Al2N2H4, which has the proper Al/N ratio expected of bulk aluminum nitrides. Novel rovibrational spectroscopic constants are computed for alane and the first two formed structures, AlNH6 and AlNH4, along the reaction pathway for use as reference in possible laboratory or observational studies. The ν 8 bending frequency for AlNH6 at 755.7 cm−1 (13.23 μm) presents a vibrational transition intensity of 515 km mol−1, more intense than the antisymmetric C−O stretch of carbon dioxide, and contains a dipole moment of 5.40 D, which is ∼3× larger than that of water. Thus, the present reaction pathway and rovibrational spectroscopic analysis may potentially assist in the astrophysical detection of novel, inorganic species which may be indicative of larger dust grain nucleation.

Boersma C., Allamandola L.J., Esposito V.J., Maragkoudakis A., Bregman J.D., Temi P., Lee T.J., Fortenberry R.C., Peeters E.

Abstract A first look is taken at the NIRSpec 1–5 μm observations from James Webb Space Telescope program 1591 that targets seven objects along the low-mass stellar life cycle with polycyclic aromatic hydrocarbon (PAH) emission. Spectra extracted from a 1.″5 radius circular aperture are explored, showing a wealth of features, including the 3 μm PAH complex, the PAH continuum, and atomic and molecular emission lines from H i, He, H2, and other species. CO2- and H2O-ice absorption and CO emission is also seen. Focusing on the bright-PDR position in M17, the PAH CH stretch falls at 3.29 μm (FWHM = 0.04 μm). Signs of its 1.68 μm overtone are confused by line emission in all targets. Multicomponent decomposition reveals a possible aliphatic deuterated PAH feature centered at 4.65 μm (FWHM = 0.02 μm), giving [D/H]alip. = 31% ± 12.7%. However, there is little sign of its aromatic counterpart between 4.36 and 4.43 μm. There is also little sign of PAH nitrile emission between 4.34 and 4.39 μm. A PAH continuum rises from ∼1 to 3.2 μm, after which it jumps by about a factor of 2.5 at 3.6 μm, with bumps at 3.8, 4.04, and 4.34 μm adding structure. The CO2 absorption band in M17 is matched with 10:1 H2O:CO2 ice at 10 K. The v = 0 pure rotational molecular hydrogen population diagram reveals >2200 K UV-pumped gas. The hydrogen Pfund series runs from levels 10 to >30. Considering Brα/Brβ = 0.381 ± 0.01966 and Case B recombination results in A V ≃ 8. CO emission in IRAS 21282+5050 originates from 258 K gas. In-depth spectral–spatial analysis of all features and targets is planned for a series of forthcoming papers.

Woon D.E.

ABSTRACT Quantum chemical cluster calculations employing density functional theory and correlation consistent basis sets reveal the following pathways by which hydroxide anions (OH–) may form in amorphous astrophysical ices: (1) hydroxyl radicals (OH), which may arise in ice via ultraviolet photolysis, can capture electrons; (2) adsorbed hydrogen atoms can capture electrons to form H–, which reacts with water to yield H2 and OH–; (3) NaOH deposited on ice dissociates into Na+ and OH–; (4) NaH deposited on ice dissociates into Na+ and H–; H– then reacts with water to yield H2 and OH– as above. The IR spectrum of ice-bound OH– is presented, based on nine clusters containing up to 31H2O and 1–2 OH– anions. The interaction of OH– in ice with cations is also explored. Prior work shows that when HCO+ is deposited on pure amorphous water clusters, it reacts with H2O to form formic acid (HCOOH) and the hydronium (H3O+). When HCO+ is deposited on a cluster containing OH–, the reaction proceeds in almost the same manner, but the H3O+ and OH– charge centres migrate through the water network toward each other and tend to neutralize one another by forming H2O. This occurred in all but one of seven cases considered; migration occurred even when the oxygen atom attacked by HCO+ is over 10 Å from the oxygen atom in OH–. Cations and anions can interact in ice via pathways not present in the gas phase or incorporated in current models.

Flint A.R., Fortenberry R.C.

Sanz-Novo M., Rivilla V.M., Jiménez-Serra I., Martín-Pintado J., Colzi L., Zeng S., Megías A., López-Gallifa Á., Martínez-Henares A., Massalkhi S., Tercero B., de Vicente P., Martín S., Andrés D.S., Requena-Torres M.A.

Abstract A quarter century after the detection of the last interstellar carboxylic acid, acetic acid (CH3COOH), we report the discovery of a new one, the cis-trans form of carbonic acid (HOCOOH), toward the Galactic center molecular cloud G+0.693–0.027. HOCOOH stands as the first interstellar molecule containing three oxygen atoms and the third carboxylic acid detected so far in the interstellar medium. Albeit the limited available laboratory measurements (up to 65 GHz), we have also directly identified several pairs of unblended lines in the astronomical data (between 75 and 120 GHz), which allowed us to slightly improve the set of spectroscopic constants. We derive a column density for cis-trans HOCOOH of N = (6.4 ± 0.4) × 1012 cm−2, which yields an abundance with respect to molecular H2 of 4.7 × 10−11. Meanwhile, the extremely low dipole moment (about 15 times lower) of the lower-energy conformer, cis-cis HOCOOH, precludes its detection. We obtain an upper limit to its abundance with respect to H2 of ≤1.2 × 10−9, which suggests that cis-cis HOCOOH might be fairly abundant in interstellar space, although it is nearly undetectable by radio astronomical observations. We derive a cis-cis/cis-trans ratio of ≤25, consistent with the smaller energy difference between both conformers compared with the relative stability of trans- and cis-formic acid. Finally, we compare the abundance of these acids in different astronomical environments, further suggesting a relationship between the chemical content found in the interstellar medium and the chemical composition of the minor bodies of the solar system, which could be inherited during the star formation process.

Law C.J., Booth A.S., Öberg K.I.

Abstract Planets form in dusty, gas-rich disks around young stars, while at the same time, the planet formation process alters the physical and chemical structure of the disk itself. Embedded planets will locally heat the disk and sublimate volatile-rich ices, or in extreme cases, result in shocks that sputter heavy atoms such as Si from dust grains. This should cause chemical asymmetries detectable in molecular gas observations. Using high-angular-resolution ALMA archival data of the HD 169142 disk, we identify compact SO J = 88 − 77 and SiS J = 19 − 18 emission coincident with the position of a ∼ 2 M Jup planet seen as a localized, Keplerian NIR feature within a gas-depleted, annular dust gap at ≈38 au. The SiS emission is located along an azimuthal arc and has a morphology similar to that of a known 12CO kinematic excess. This is the first tentative detection of SiS emission in a protoplanetary disk and suggests that the planet is driving sufficiently strong shocks to produce gas-phase SiS. We also report the discovery of compact 12CO and 13CO J = 3 − 2 emission coincident with the planet location. Taken together, a planet-driven outflow provides the best explanation for the properties of the observed chemical asymmetries. We also resolve a bright, azimuthally asymmetric SO ring at ≈24 au. While most of this SO emission originates from ice sublimation, its asymmetric distribution implies azimuthal temperature variations driven by a misaligned inner disk or planet–disk interactions. Overall, the HD 169142 disk shows several distinct chemical signatures related to giant planet formation and presents a powerful template for future searches of planet-related chemical asymmetries in protoplanetary disks.

Westbrook B.R., Fortenberry R.C.

Campanha D.R., Mendoza E., Silva M.X., Velloso P.F., Carvajal M., Wakelam V., Galvão B.R.

ABSTRACT The Si + SO2 reaction is investigated to verify its impact on the abundances of molecules with astrochemical interest, such as SiS, SiO, SO, and others. According to our results Si(3P) and SO2 react barrierlessly yielding only the monoxides SO and SiO as products. No favourable pathway has been found leading to other products, and this reaction should not contribute to SiS abundance. Furthermore, it is predicted that SiS is stable in collisions with O2, and that S(3P) + SiO2 and O(3P)+OSiS will also produce SO + SiO. Using these results and gathering further experimental and computational data from the literature, we provide an extended network of neutral–neutral reactions involving Si- and S-bearing molecules. The effects of these reactions were examined in a protostellar shock model, using the nautilus gas–grain code. This consisted in simulating the physicochemical conditions of a shocked gas evolving from (i) primeval cold core, (ii) the shock region itself, (iii) and finally the gas bulk conditions after the passage of the shock. Emphasizing on the cloud ages and including systematically these chemical reactions, we found that [SiS/H2] can be of the order of ∼10−8 in shocks that evolves from clouds of t = 1 × 106 yr, whose values are mostly affected by the SiS + O $\longrightarrow$SiO + S reaction. Perspectives on further models along with observations are discussed in the context of sources harbouring molecular outflows.

McGuire B.A.

Abstract To date, 241 individual molecular species, composed of 19 different elements, have been detected in the interstellar and circumstellar medium by astronomical observations. These molecules range in size from two atoms to 70 and have been detected across the electromagnetic spectrum from centimeter wavelengths to the ultraviolet. This census presents a summary of the first detection of each molecular species, including the observational facility, wavelength range, transitions, and enabling laboratory spectroscopic work, as well as listing tentative and disputed detections. Tables of molecules detected in interstellar ices, external galaxies, protoplanetary disks, and exoplanetary atmospheres are provided. A number of visual representations of these aggregate data are presented and briefly discussed in context.

Grosselin D., Fortenberry R.C.

Watrous A.G., Westbrook B.R., Fortenberry R.C.

The F12-TZ-cCR quartic force field (QFF) methodology, defined here as CCSD(T)-F12b/cc-pCVTZ-F12 with further corrections for relativity, is introduced as a cheaper and even more accurate alternative to more costly composite QFF methods like those containing complete basis set extrapolations within canonical coupled cluster theory. F12-TZ-cCR QFFs produce B0 and C0 vibrationally averaged principal rotational constants within 7.5 MHz of gas-phase experimental values for tetraatomic and larger molecules, offering higher accuracy in these constants than the previous composite methods. In addition, F12-TZ-cCR offers an order of magnitude decrease in the computational cost of highly accurate QFF methodologies accompanying this increase in accuracy. An additional order of magnitude in cost reduction is achieved in the F12-DZ-cCR method, while also matching the accuracy of the traditional composite method's B0 and C0 constants. Finally, F12-DZ and F12-TZ are benchmarked on the same test set, revealing that both methods can provide anharmonic vibrational frequencies that are comparable in accuracy to all three of the more expensive methodologies, although their rotational constants lag behind. Hence, the present work demonstrates that highly accurate theoretical rovibrational spectral data can be obtained for a fraction of the cost of conventional QFF methodologies, extending the applicability of QFFs to larger molecules.

Fortenberry R.C.

Rey-Montejo M., Jiménez-Serra I., Martín-Pintado J., Rivilla V.M., Megías A., Andrés D.S., Sanz-Novo M., Colzi L., Zeng S., López-Gallifa Á., Martínez-Henares A., Martín S., Tercero B., de Vicente P., Requena-Torres M.

Abstract We report the first detection of the metal-bearing molecules sodium sulfide and magnesium sulfide and the tentative detection of calcium monoxide in the interstellar medium toward the Galactic center molecular cloud G+0.693-0.027. The derived column densities are (5.0 ± 1.1) × 1010 cm−2, (6.0 ± 0.6) × 1010 cm−2, and (2.0 ± 0.5) × 1010 cm−2, respectively. This translates into fractional abundances with respect to H2 of (3.7 ± 1.0) × 10−13, (4.4 ± 0.8) × 10−13, and (1.5 ± 0.4) × 10−13, respectively. We have also searched for other Na-, Mg-, and Ca-bearing species toward this source but none of them have been detected and thus we provide upper limits for their abundances. We discuss the possible chemical routes involved in the formation of these molecules containing metals under interstellar conditions. Finally, we compare the ratio between sulfur-bearing and oxygen-bearing molecules with and without metals, finding that metal-bearing sulfur molecules are much more abundant than metal-bearing oxygen ones, in contrast with the general trend found in the ratios between other nonmetal-oxygen- and sulfur-bearing molecules. This further strengthens the idea that sulfur may be a little depleted in G+0.693-0.027 as a result of the low-velocity shocks present in this source sputtering large amounts of material from dust grains.

Firth R.A., Fortenberry R.C.

One of the most abundant Al-containing molecules detected in the interstellar medium (ISM) is AlOH. Over the past several years, there have been various pathways proposed for the formation of AlOH in the ISM, including reactions between AlO and H2 or H2O. However, these pathways include an energetic barrier from a transition state that likely prevents the reaction from progressing efficiently in the low temperature/low pressure environment of the ISM. Recently, a barrierless pathway for formation of AlOH from AlO and AlH has been proposed for the formation of AlOH. Even so, only one of these species really needs to contain an aluminum atom. To account for this, alternative but related pathways reacting the known interstellar molecule AlO with XH and AlH with XO (X = Mg, Si, P, or S) to form AlOH are explored with high accuracy quantum chemical calculations via CCSD(T)-F12b/cc-pVTZ-F12. Each third row element has at least one pair of reactants that lead to exothermic formation of AlOH. These reactions can go on to form other aluminum oxides and aluminum oxide clusters that may, in part, lead to the formation of interstellar dust grains.