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Despite its importance in planet formation and biology¹, phosphorus has been identified only in the inner 12 kpc of the Galaxy^2–19. The study of this element has been hindered in part by unfavourable atomic transitions^2,4,20. Phosphorus is thought to be created by neutron capture on²⁹Si and³⁰Si in massive stars^20,21, and released into the interstellar medium by Type II supernova explosions^2,22. However, models of galactic chemical evolution must arbitrarily increase the supernovae production²³to match observed abundances. Here we present the detection of gas-phase phosphorus in the Outer Galaxy through millimetre spectra of PO and PN. Rotational lines of these molecules were observed in the dense cloud WB89-621, located 22.6 kpc from the Galactic Centre²⁴. The abundances of PO and PN in WB89-621 are comparable to values near the Solar System²⁵. Supernovae are not present in the Outer Galaxy²⁶, suggesting another source of phosphorus, such as ‘Galactic Fountains’, where supernova material is redistributed through the halo and circumgalactic medium²⁷. However, fountain-enriched clouds are not found at such large distances. Any extragalactic source, such as the Magellanic Clouds, is unlikely to be metal rich²⁸. Phosphorus instead may be produced by neutron-capture processes in lower mass asymptotic giant branch stars²⁹which are present in the Outer Galaxy. Asymptotic giant branch stars also produce carbon²¹, flattening the extrapolated metallicity gradient and accounting for the high abundances of C-containing molecules in WB89-621.

 

A new interstellar molecule, FeC (X³Δ_i), has been identified in the circumstellar envelope of the carbon-rich asymptotic giant branch star IRC+10216. FeC is the second iron-bearing species conclusively observed in the interstellar medium, in addition to FeCN, also found in IRC+10216. TheJ= 4 → 3, 5 → 4, and 6 → 5 rotational transitions of this free radical near 160, 201, and 241 GHz, respectively, were detected in the lowest spin–orbit ladder, Ω = 3, using the Submillimeter Telescope of the Arizona Radio Observatory (ARO) for the 1 mm lines and the ARO 12 m at 2 mm. Because the ground state of FeC is inverted, these transitions are the lowest energy lines. The detected features exhibit slight U shapes with LSR velocities nearV_LSR≈ −26 km s⁻¹and linewidths of ΔV_1/2≈ 30 km s⁻¹, line parameters characteristic of IRC+10216. Radiative transfer modeling of FeC suggests that the molecule has a shell distribution with peak radius near 300R_*(∼6″) extending out to ∼500R_*(∼10″) and a fractional abundance, relative to H₂, off∼ 6 × 10⁻¹¹. The previous FeCN spectra were also modeled, yielding an abundance off∼ 8 × 10⁻¹¹in a larger shell situated near 800R_*. These distributions suggest that FeC may be the precursor species for FeCN. Unlike cyanides and carbon-chain molecules, diatomic carbides with a metallic element are rare in IRC+10216, with FeC being the first such detection.

 

TheJ= 2 → 1 transition of CO near 230 GHz and theJ= 3 → 2 line of HCN at 265 GHz have been imaged in the envelope of the red hypergiant star, VY Canis Majoris (VY CMa), using the Atacama Large Millimeter Array (ALMA) with angular resolutions 0.″2–1.″5; single-dish data were added to provide sensitivity up to 30″. These images reveal a far more complex envelope, with previously unseen outflows extending 4″–9″ from the star. These new structures include an arc-like outflow with an angular separation of ∼9″ northeast from the stellar position (“NE Arc”), twin fingerlike features approximately 4″ to the north/northeast (“NE Extension”), and a roughly spherical region observed ∼7″ E of the star (“E Bubble”). The NE Arc appears to be decelerating from base (V_LSR∼ 7 km s⁻¹) to tip (V_LSR∼ 18 km s⁻¹), while the NE Extension is blueshifted withV_LSR∼ −7 km s⁻¹. Among the new features, HCN is only detected in the NE Arc. In addition, known structures Arc 1, Arc 2, and NW Arc, as well as other features closer to the star, are closely replicated in CO, suggesting that the gas and dust are well mixed. The CO spectra are consistent with the kinematic picture of VY CMa derived from HST data. Arc 2, however, has added complexity. Preliminary results from CO suggest¹²C/¹³C ∼ 22–38 across the envelope. The additional presence of at least three major episodic mass ejection events significantly broadens the current perspective of the envelope structure and mass-loss history of VY CMa.

 

A sensitive (1σrms ≤ 3 mK; 2 MHz resolution) 1 mm spectral survey (214.5–285.5 GHz) of the envelope of the oxygen-rich supergiant star NML Cygni (NML Cyg) has been conducted using the 10 m Submillimeter Telescope of the Arizona Radio Observatory. These data represent the first spectral line survey of NML Cyg and are complementary to a previous 1 mm survey of the envelope of a similar hypergiant, VY Canis Majoris (VY CMa). The complete NML Cyg data set is presented here. In the survey, 104 emission lines were observed, arising from 17 different molecules and 4 unidentified features. Many of the observed features have complex line profiles, arising from asymmetric outflows characteristic of hypergiant stars. While most of the lines in the survey arise from SiO, SO, SO₂, and SiS, CO had the strongest emission. Five other C-bearing species are identified in the survey (HCN, CN, HCO⁺, CS, and HNC), demonstrating an active carbon chemistry despite the O-rich environment. Moreover, NS was observed, but not NO, although favorable transitions of both molecules lie in the surveyed region. Sulfur chemistry appears to be prominent in NML Cyg and plays an important role in the collimated outflows. The refractory species observed, NaCl and AlO, have narrow emission lines, indicating that these molecules do not reach the terminal expansion velocity. NaCl and AlO likely condense into dust grains at r < 50R_*. From NaCl, the chlorine isotope ratio was determined to be³⁵Cl/³⁷Cl = 3.85 ± 0.30.

 

The millimeter-wave spectrum of the SiP radical (X²Π_i) has been measured in the laboratory for the first time using direct-absorption methods. SiP was created by the reaction of phosphorus vapor and SiH₄in argon in an AC discharge. Fifteen rotational transitions (J+ 1 ←J) were measured for SiP in the Ω = 3/2 ladder in the frequency range 151–533 GHz, and rotational, lambda doubling, and phosphorus hyperfine constants determined. Based on the laboratory measurements, SiP was detected in the circumstellar shell of IRC+10216, using the Submillimeter Telescope and the 12 m antenna of the Arizona Radio Observatory at 1 mm and 2 mm, respectively. Eight transitions of SiP were searched: four were completely obscured by stronger features, two were uncontaminated (J= 13.5 → 12.5 and 16.5 → 15.5), and two were partially blended with other lines (J= 8.5 → 7.5 and 17.5 → 16.5). The SiP line profiles were broader than expected for IRC+10216, consistent with the hyperfine splitting. From non-LTE radiative transfer modeling, SiP was found to have a shell distribution with a radius ∼300R_*, and an abundance, relative to H₂, off∼ 2 × 10⁻⁹. From additional modeling, abundances of 7 × 10⁻⁹and 9 × 10⁻¹⁰were determined for CP and PN, respectively, both located in shells at 550–650R_*. SiP may be formed from grain destruction, which liberates both phosphorus and silicon into the gas phase, and then is channeled into other P-bearing molecules such as PN and CP.

 

The millimeter/submillimeter-wave spectrum of the SiP radical (X 2 Π i ) has been recorded using direct absorption spectroscopy in the frequency range of 151–532 GHz. SiP was synthesized in an AC discharge from the reaction of SiH 4 and gas-phase phosphorus, in argon carrier gas. Both spin–orbit ladders were observed. Fifteen rotational transitions were measured originating in the Ω = 3/2 ladder, and twelve in the Ω = 1/2 substate, each exhibiting lambda doubling and, at lower frequencies, hyperfine interactions from the phosphorus nuclear spin of I = 1/2. The lambda-doublets in the Ω = 1/2 levels appeared to be perturbed at higher J, with the f component deviating from the predicted pattern, likely due to interactions with the nearby excited A 2 Σ + electronic state, where ΔE Π-Σ ∼ 430 cm −1 . The data were analyzed using a Hund’s case a β Hamiltonian and rotational, spin–orbit, lambda-doubling, and hyperfine parameters were determined. A 2 Π/ 2 Σ deperturbation analysis was also performed, considering spin–orbit, spin-electronic, and L-uncoupling interactions. Although SiP is clearly not a hydride, the deperturbed parameters derived suggest that the pure precession hypothesis may be useful in assessing the 2 Π/ 2 Σ interaction. Interpretation of the Fermi contact term, b F , the spin-dipolar constant, c, and the nuclear spin-orbital parameter, a, indicates that the orbital of the unpaired electron is chiefly p π in character. The bond length in the v = 0 level was found to be r 0 = 2.076 Å, suggestive of a double bond between the silicon and phosphorus atoms. 

The detection of the fullerenes C60 and C70 in the interstellar medium (ISM) has transformed our understanding of chemical complexity in space. These discoveries also raise the possibility for the presence of even larger molecules in astrophysical environments. Here we report in situ heating of analog silicon carbide (SiC) presolar grains using transmission electron microscopy (TEM). These heating experiments are designed to simulate the temperature conditions occurring in post-AGB stellar envelopes. Our experimental findings reveal that heating the analog SiC grains to the point of decomposition initially yields hemispherical C60-sized nanostructures, with five- and six-membered rings, which transform into multiwalled carbon nanotubes (MWCNTs) if held isothermally >2 min. These MWCNTs are certainly larger than any of the currently observed interstellar fullerene species, both in overall size and number of C atoms. These experimental simulations suggest that such MWCNTs are likely to form in post-AGB circumstellar material, where the structures, along with the smaller fullerenes, are subsequently injected into the ISM. 

Understanding the fundamental mechanisms that underlie the synthesis of fullerene molecules in the interstellar medium (ISM) and in the environments of astrophysical objects is an open question. In this regard, using classical molecular dynamics, we demonstrate the possibility of in situ formation of fullerene molecules, such as C 60 from graphite, which is known to occur in the ISM, in particular, circumstellar environments. Specifically, when graphite is subjected to thermal and mechanical stimuli that are typical of circumstellar shells, we find that the graphite sheet edges undergo significant restructuring and curling, leading to edge-induced interlayer-interactions and formation of mechanically strained five-membered-ring structural units. These units serve as precursors for the formation of fullerene structures, such as pristine and metastable C 60 molecules. The pathways leading to molecular C 60 formation consist of a series of steps that involve bond-breakage and subsequent local rearrangement of atoms, with the activation energy barriers of the rate-limiting step(s) being comparable to the energetics of Stone–Wales rearrangement reactions. The identified chemical pathways provide fundamental insights into the mechanisms that underlie C 60 formation. Moreover, they clearly demonstrate that top-down synthesis of C 60 from graphitic sources is a viable synthesis route at conditions pertaining to circumstellar matter. 

Abstract Observations of HCN and HCO + have been carried out toward 13 planetary nebulae (PNe) using the facilities of the Arizona Radio Observatory (ARO). These nebulae represent a wide range of morphologies and ages (∼2000–28,000 yr). For both molecules, the J = 1 → 0 transitions at 88–89 GHz and the J = 3 → 2 lines at 265–267 GHz were measured, together with CO lines ( J = 1 → 0, 2 → 1, and 3 → 2, depending on the source), using the ARO 12 m and Submillimeter Telescopes. HCN and HCO + were detected with at least one transition in 10 nebulae: He 2-459, Hu 1-1, K3-52, K3-65, M1-8, M1-40, M1-59, M2-53, M4-17, and NGC 6445. HCO + was additionally identified via two transitions in Na 2. Some observed line profiles were complex, with multiple velocity components tracing varied outflows. From radiative transfer modeling, column densities were established for HCN and HCO + : N tot (HCN) = 0.005–1.1 × 10 14 and N tot (HCO + ) = 0.008–9.5 × 10 13 cm −2 . Gas densities of n (H 2 ) ∼ 10 5 –10 7 cm −3 were also determined for all PNe. Fractional abundances with respect to H 2 , calculated using CO as a proxy, are f (HCN) ∼ 0.2–1.5 × 10 −7 and f (HCO + ) ∼ 0.3–5.1 × 10 −8 . The abundances of HCN and HCO + did not significantly vary with nebular age to 28,000 yr. Combined with previous observations, at least 30 PNe contain HCN and/or HCO + , indicating that polyatomic molecules are common constituents of these objects. The data strongly support a scenario where dense ejecta from PNe seed the interstellar medium with molecular material.