Rotational Transitions Research Articles

Millimeter-Wave and High-Resolution Infrared Spectroscopy of 3-Furonitrile.

The rotational spectrum of 3-furonitrile has been collected from 85 to 500 GHz, spanning the most intense rotational transitions observable at room temperature. The large dipole moment imparted by the nitrile substituent confers substantial intensity to the rotational spectrum, enabling the observation of over 5600 new rotational transitions. Combined with previously published transitions, the available data set was least-squares fit to partial-octic, distorted-rotor A- and S-reduced Hamiltonian models with low statistical uncertainty (σfit < 0.031 MHz) for the ground vibrational state. Similar to its isomer 2-furonitrile, the two lowest-energy vibrationally excited states of 3-furonitrile (ν17, ν24), which correspond to the in-plane and out-of-plane nitrile bending vibrations, form an a- and b-axis Coriolis-coupled dyad. Rotationally resolved infrared transitions (30-600 cm-1) and over 4200 pure rotational transitions for both ν17 and ν24 were fit to a partial-octic, Coriolis-coupled, two-state Hamiltonian with low statistical uncertainty (σfit rot < 0.045 MHz, σfit IR < 6.1 MHz). The least-squares fitting of these vibrationally excited states provides their accurate and precise vibrational frequencies (ν17 = 168.193 164 8 (67) cm-1 and ν24 = 169.635 831 5 (77) cm-1) and seven Coriolis-coupling terms (Ga, GaJ, GaK, Fbc, FbcK, Gb, and Fac). The two fundamental states exhibit a notably small energy gap (1.442 667 (10) cm-1) and an inversion of the relative energies of ν17 and ν24 compared to those of the isomer 2-furonitrile. The rotational frequencies and spectroscopic constants of 3-furonitrile that we present herein provide a sufficient basis for conducting radioastronomical searches for this molecule across the majority of the frequency range available to current radiotelescopes.

JWST Observations of Young protoStars (JOYS)

Context. Accretion and ejection dictate the outcomes of star and planet formation processes. The mid-infrared (MIR) wavelength range offers key tracers of processes that have been difficult to detect and spatially resolve in protostars until now. Aims. We aim to characterize the interplay between accretion and ejection in the low-mass Class I protobinary system TMC1, comprising two young stellar objects: TMC1-W and TMC1-E at a 85 au separation. Methods. Using the James Webb Space Telescope (JWST) Mid-Infrared Instrument (MIRI) observations in 5–28 μm range, we measured the intensities of emission lines of H2, atoms, and ions, for instance, the [Fe II] and [Ne II], and HI recombination lines. We analyzed the spatial distribution of the different species using the MIRI Medium Resolution Spectrometer (MRS) capabilities to spatially resolve emission at 0″​​.2–0″​​.7 scales. we compared these results with the corresponding Atacama Large Millimeter/submillimeter Array (ALMA) maps tracing cold gas and dust. Results. We detected H2 outflow coming from TMC1-E, with no significant H2 emission from TMC1-W. The H2 emission from TMC1-E outflow appears narrow and extends to wider opening angles with decreasing Eup from S(8) to S(1) rotational transitions, indicating the disk wind as its origin. The outflow from TMC1-E protostar shows spatially extended emission lines of [Ne II], [Ne III], [Ar II], and [Ar III], with their line ratios consistent with UV radiation as a source of ionization. With ALMA, we detected an accretion streamer infalling from &gt; 1000 au scales onto the TMC1-E component. The TMC1-W protostar powers a collimated jet, detected with [Fe II] and [Ni II], making it consistent with energetic flow. A much weaker ionized jet is observed from TMC1-E, and both jets appear strikingly parallel to each other, indicating that the disks are co-planar. TMC1-W is associated with strong emission from hydrogen recombination lines, tracing the accretion onto the young star. Conclusions. MIRI-MRS observations provide an unprecedented view of protostellar accretion and ejection processes on 20 au scales. Observations of a binary Class I protostellar system show that the two processes are clearly intertwined, with accretion from the envelope onto the disk influencing a wide-angle wind ejected on disk scales. Finally, the accretion from the protostellar disk onto the protostar is associated with the source launching a collimated high-velocity jet within the innermost regions of the disk.

Two-photon laser-induced fluorescence study of the CO B 1Σ+ (v' = 0) state in a 4850K plasma plume: Modified molecular constants, evidence of predissociation, and J'-dependent photoionization.

We report the two-photon absorption laser-induced fluorescence rotational spectrum of the CO B 1Σ+ ← X 1Σ+ Hopfield-Birge system (v' = 0, v″ = 0) Q-branch in an ∼4850K, atmospheric pressure plasma torch plume at thermal equilibrium in both the quenching-dominated (low laser intensity) and photoionization-dominated (high laser intensity) regimes. We provide a detailed analysis of the photophysics in these two regimes using a rate equation approach and propose modeling considerations for them as well. In the experimental spectra, distinct rotational transitions up to J″ = 83 are observed, allowing analysis over a very large range of rotational states. Evidence of predissociation is observed for J' ≥ 64 and is likely due to the interaction with the D'1Σ+ electronic state, which has been proposed in the literature but never observed in the v' = 0 state. The line positions of higher rotational states show disagreement with line positions calculated from molecular constants in the available literature, suggesting the need for modifications to the constants, which are reported here. A shift in the B 1Σ+ ← X 1Σ+ absorption spectrum toward higher two-photon energy as a result of the second-order Stark shift was observed in the photoionization-dominated spectrum, and the second-order Stark shift cross section was estimated to be 7 ± 3 × 10-18 cm2. The mean photoionization cross section of the excited upper state was inferred by comparing the line broadening of the two spectra and was estimated to be 11 ± 7 × 10-18 cm2. In addition, weak J'-dependent variations of the photoionization cross section were observed and are reported here.

Atacama Large Aperture Submillimeter Telescope (AtLAST) science: The hidden circumgalactic medium.

Our knowledge of galaxy formation and evolution has incredibly progressed through multi-wavelength observational constraints of the interstellar medium (ISM) of galaxies at all cosmic epochs. However, little is known about the physical properties of the more diffuse and lower surface brightness reservoir of gas and dust that extends beyond ISM scales and fills dark matter haloes of galaxies up to their virial radii, the circumgalactic medium (CGM). New theoretical studies increasingly stress the relevance of the latter for understanding the feedback and feeding mechanisms that shape galaxies across cosmic times, whose cumulative effects leave clear imprints into the CGM. Recent studies are showing that a - so far unconstrained - fraction of the CGM mass may reside in the cold ( T < 10 4 K) molecular and atomic phase, especially in high-redshift dense environments. These gas phases, together with the warmer ionised phase, can be studied in galaxies from z ∼ 0 to z ∼ 10 through bright far-infrared and sub-millimeter emission lines such as [C ii] 158 µm, [O iii] 88 µm, [C I] 609 µm, [C i] 370 µm, and the rotational transitions of CO. Imaging such hidden cold CGM can lead to a breakthrough in galaxy evolution studies but requires a new facility with the specifications of the proposed Atacama Large Aperture Submillimeter Telescope (AtLAST). In this paper, we use theoretical and empirical arguments to motivate future ambitious CGM observations with AtLAST and describe the technical requirements needed for the telescope and its instrumentation to perform such science.

Glassy dynamics in a liquid of anisotropic molecules: Bifurcation of relaxation spectrum

In experimental and theoretical studies of glass transition phenomena, one often finds a sharp crossover in dynamical properties at a temperature Tcr. A bifurcation of a relaxation spectrum is also observed at a temperature TB≈Tcr; both lie significantly above the glass transition temperature. In order to better understand these phenomena, we introduce a new model of glass-forming liquids, a binary mixture of prolate and oblate ellipsoids. This model system exhibits sharp thermodynamic and dynamic anomalies, such as the specific heat jump during heating and a sharp variation in the thermal expansion coefficient around a temperature identified as the glass transition temperature, Tg. The same temperature is obtained from the fit of the calculated relaxation times to the Vogel–Fulcher–Tammann (VFT) form. As the temperature is lowered, the calculated single peak rotational relaxation spectrum splits into two peaks at TB above the estimated Tg. Similar bifurcation is also observed in the distribution of short-to-intermediate time translational diffusion. Interrogation of the two peaks reveals a lower extent of dynamic heterogeneity in the population of the faster mode. We observe an unexpected appearance of a sharp peak in the product of rotational relaxation time τ2 and diffusion constant D at a temperature Tcr, close to TB, but above the glass transition temperature. Additionally, we coarse-grain the system into cubic boxes, each containing, on average, ∼62 particles, to study the average dynamical properties. Clear evidence of large-scale sudden changes in the diffusion coefficient and rotational correlation time signals first-order transitions between low and high-mobility domains.

Vibrational Relaxation of D2O Induced by Collision with He: A Rigid Bender Close Coupling Study.

The vibrational relaxation of the first excited bending state of D2O induced by collision with He is studied at the close coupling level and using the Rigid Bender approximation. A new 4D potential energy surface is calculated and reported for this system. It is then used to determine the low-lying bound states of the D2O-He van der Waals complex and to perform scattering calculations. Collision rates are determined for pure rotational transitions as well as for rovibrational transitions within the first excited bending state. The results are compared with those obtained for the collision of D2O with other noble gases such as Ne and Ar. We also analyse the differences observed with respect to the H2O+He collisions and compare our results with experiment.

Fourier transform microwave spectroscopy of the 13C- and 18O-substituted tropolone. Proton tunneling effect for the isotopic species with the asymmetric potential wells.

Fourier-transform microwave spectroscopy has been applied for the 13C/18O-substituted tropolone to observe tunneling-rotation transitions as well as pure rotational transitions. The tunneling-rotation transitions were observed between the 13C-4 and -6 forms as well as between 13C-3 and -7, between 13C-1 and -2, and between 18O-8 and -9 (we denote these tunneling pairs as 13C-46, etc., below) although they have an asymmetric tunneling potential due to the difference in the zero point energy (ZPE). From the observed tunneling splittings ΔEij (0.9800-1.6824 cm-1), the differences in ZPE Δij for the 13C-46, -37, -12, and 18O-89 species are derived to be -0.1104, 0.5652, -1.3682, and 1.3897 cm-1 to agree well with the DFT calculation. The state mixing ratio of the tunneling states decreases drastically from (44%:56%) to (8.7%:91.3%) for 13C-46 and 18O-89 with an increase in the asymmetry Δij of the tunneling potential function. The observed tunneling-rotation interaction constants Fij decrease from 16.001 to 9.224 cm-1 as the differences in ZPE Δij increase, while the diagonal tunneling-rotation interaction constants Fu increase from 1.767 to 13.70 cm-1, explained well by the mixing ratio of the tunneling states.

Rotational inertia-induced glassy transition in chiral particle systems.

The dense active matter exhibits characteristics reminiscent of traditional glassy phenomena, yet the role of rotational inertia in glass dynamics remains elusive. In this study, we investigate the glass dynamics of chiral active particles influenced by rotational inertia. Rotational inertia endows exponential memory to particle orientation, restricting its alteration and amplifying the effective persistence time. At lower spinning frequencies, the diffusion coefficient exhibits a peak function relative to rotational inertia for shorter persistence times, while it steadily increases with rotational inertia for longer persistence times. In the realm of high-frequency spinning, the impact of rotational inertia on diffusion behavior becomes more pronounced, resulting in a nonmonotonic and intricate relationship between the diffusion coefficient and rotational inertia. Consequently, the introduction of rotational inertia significantly alters the glassy dynamics of chiral active particles, allowing for the control over transitions between fluid and glassy states by modulating rotational inertia. Moreover, our findings indicate that at a specific spinning temperature, there exists an optimal spinning frequency at which the diffusion coefficient attains its maximum value.

Laboratory and astronomical discovery of cyanothioketene, NCCHCS, in the cold starless core TMC-1

We present the detection of cyanothioketene, NCCHCS, in the laboratory and toward TMC-1. This transient species was produced through a discharge of a gas mixture of CH2CHCN and CS2 using argon as carrier gas, and its rotational spectrum between 9 and 40 GHz was characterized using a Balle-Flygare narrowband-type Fourier-transform microwave spectrometer. A total of 21 rotational transitions were detected in the laboratory, all of them exhibiting hyperfine structure induced by the spin of the N nucleus. The spectrum for NCCHCS was predicted in the domain of our line surveys using the derived rotational and distortion constants. The detection in the cold starless core TMC-1 was based on the QUIJOTE1 line survey performed with the Yebes 40 m radio telescope. Twenty-three lines were detected with Ka = 0, 1, and 2 and Ju = 9 up to 14. The derived column density is (1.2 ± 0.1)×1011 cm−2 for a rotational temperature of 8.5 ± 1.0 K. The abundance ratio of thioketene and its cyano derivative, H2CCS/NCCHCS, is 6.5 ± 1.3. Although ketene is more abundant than thioketene by ∼15 times, its cyano derivative NCCHCO surprisingly is not detected with a 3σ upper level to the column density of 3.0 × 1010 cm−2, which results in an abundance ratio H2CCO/NCCHCO &gt; 430. Hence, the chemistry of CN derivatives seems to be more favored for S-bearing than for O-bearing molecules. We carried out chemical modeling calculations and found that the gas-phase neutral-neutral reactions CCN + H2CS and CN + H2CCS could be a source of NCCHCS in TMC-1.

Manipulating molecular rotational wave packets with resonant terahertz pulses

We found the phase differences of the expansion coefficients in rotational wave packet are in linear relationships with the phases of corresponding pulses when gas-phase linear molecules are irradiated by pulses in resonant with their rotational transitions. Using these relationships, we can accurately control the wave packet by first determine the phases of the controlling pulses, and then optimize the durations (or amplitudes) of the pulses to demanded population. We also compared the phase relationships obtained from ground and other initial rotational eigenstates and analyzed the reason for lowered orientation degree in non-zero temperature conditions.

First Detection in Space of the High-energy Isomer of Cyanomethanimine: H2CNCN

We report the first detection in the interstellar medium of N-cyanomethanimine (H2CNCN), the stable dimer of HCN of highest energy and the most complex organic molecule identified in space containing the prebiotically relevant NCN backbone. We have identified a plethora of a-type rotational transitions with 3 ≤ J up ≤ 11 and K a ≤ 2 that belong to this species toward the Galactic center G+0.693-0.027 molecular cloud, the only interstellar source showing the three cyanomethanimine isomers (including the Z- and E-isomers of C-cyanomethanimine, HNCHCN). We have derived a total column density for H2CNCN of (2.9 ± 0.1) × 1012 cm−2, which translates into a total molecular abundance with respect to H2 of (2.1 ± 0.3) × 10−11. We have also revisited the previous detection of E- and Z-HNCHCN and found a total C/N-cyanomethanimine abundance ratio of 31.8 ± 1.8 and a Z/E-HNCHCN ratio of 4.5 ± 0.2. While the latter can be explained on the basis of thermodynamic equilibrium, chemical kinetics are more likely responsible for the observed C/N-cyanomethanimine abundance ratio, where the gas-phase reaction between methanimine (CH2NH) and the cyanogen radical (CN) arises as the primary formation route.

Revisiting the rovibrational (de-)excitation of molecular hydrogen by helium

Context. The collisional (de-)excitation of H2 by He plays an important role in the thermal balance and chemistry of various astro-physical environments, making accurate rate coefficients essential for interpreting observations of the interstellar medium. Aims. Our goal is to utilize a state-of-the-art potential energy surface (PES) to provide comprehensive state-to-state rate coefficients for He-induced transitions among rovibrational levels of H2. Methods. We performed quantum scattering calculations for the H2-He system. Thus, we were able to provide state-to-state rate coefficients for 1059 transitions between rovibrational levels of H2, with internal energies up to ≃15 000 cm−1, for temperatures ranging from 20 to 8000 K. Results. Our results demonstrate a good agreement with previous calculations for pure rotational transitions between low-lying rotational levels. However, we do find significant discrepancies for rovibrational processes involving highly-excited rotational and vibrational states. We attribute these differences to two key factors: (1) the broader range of intramolecular distances covered by ab initio points and (2) the superior accuracy of the PES, resulting from the utilization of the state-of-the-art quantum chemistry methods, compared to previous lower-level calculations. Conclusions. Radiative transfer calculations performed with the new collisional data indicate that the population of rotational levels in excited vibrational states experiences significant modifications, highlighting the critical need for this updated dataset in models of high-temperature astrophysical environments.

Rotational spectrum, structure, and quadrupole coupling of cyclopropylchloromethyldifluorosilane.

Cyclopropylchloromethyldifluorosilane, c-C3H5SiF2CH2Cl, has been synthesized, and its rotational spectrum has been recorded by chirped-pulse Fourier transform microwave spectroscopy. The spectral analysis of several isotopologues indicates the presence of two distinct conformations in the free-jet expansion, which are interconvertible through a rotation of the chloromethyl group. A partial substitution structure is presented for the lower energy conformation and is compared to the equilibrium structure obtained from quantum chemical calculations. Additionally, the presence of the chlorine nucleus leads to the rotational transitions splitting into multiple hyperfine components and χaa, a measure of the electric field gradient along the a axis, is unusually small at merely +0.1393(73) MHz. Various common abinitio and density functional theory methods fail to predict good quadrupole coupling constants (in the principal axis system) that adequately reproduce the observed hyperfine splitting, although diagonalizing the quadrupole coupling tensor from the principal axis system into a nucleus-centered axis system reveals that, overall, these methods calculate reasonably the electric field gradient about the chlorine nucleus. Finally, a total of nine electric dipole forbidden, quadrupole allowed transitions are observed in the rotational spectra of the parent species of the higher energy conformation and the 37Cl isotopologue of the lower energy conformation. These include those of x-type (no change in parity of Ka or Kc), which, to our knowledge, is the first time such transitions have been observed in a chlorine-containing molecule.

Identification of Two Stable Side-Chain Orientations of Valine Methyl Ester by Microwave Spectroscopy.

The rotational spectra of two valine methyl ester (ValOMe) conformers have been measured using a cavity-based Fourier-transform microwave spectrometer in the range of 9-18 GHz. Ten conformers of ValOMe were modeled using the ωB97XD/6-311++G(d,p) level of theory, and separate spectra arising from two lowest-energy conformations were observed and assigned. 44 rotational transitions were assigned to conformer I, the lowest-energy configuration, and were fit to Watson's A-reduced Hamiltonian: A = 2552.0145(5) MHz, B = 1041.8216(3) MHz, and C = 938.54890(22) MHz. 14N nuclear quadrupole hyperfine splittings were resolved, and 231 hyperfine components were fit to χaa = -4.187(7) MHz, and χbb-χcc = 1.269(5) MHz. The spectrum of conformer I also reveals tunneling splittings arising from the methyl rotor. XIAM was used to fit the barrier to the internal rotation of the methyl rotor, and the best-fit V3 barrier was found to be 401.64(19) cm-1. 47 rotational transitions were assigned for conformer II (ΔE = 2.08 kJ mol-1), and the fitted rotational constants are A = 2544.2837(3) MHz, B = 1092.3654(15) MHz, and C = 896.3131(12) MHz. 264 hyperfine components were fit to χaa = -4.187(7) MHz and χbb-χcc = 1.518(6) MHz, and the best-fit V3 barrier was found to be 409.74(16) cm-1.

Unlocking a new hydrogen-bonding marker: C-O bond shortening in vicinal diols revealed by rotational spectroscopy.

The conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol-1 were identified computationally. A rotational spectrum of jet-cooled cis-1,2-cyclohexanediol was recorded with a chirped pulse Fourier transform microwave spectrometer. Two sets of rotational transitions were observed and could be assigned to conformers of cis-1,2-cyclohexanediol. The non-observation of other low energy conformers was explained by conformational conversion barrier height calculations and results from experimental spectra recorded with different carrier gases. Eight isotopologues, including those with 13C and 18O, of the lowest energy conformer were observed, allowing the determination of the semi-experimental equilibrium structure, reSE. Interestingly, the structural analysis revealed that the C-O bond length of the intramolecular hydrogen-bond donor is shorter than that of the acceptor. This appears to be a general characteristic of vicinal diols and can be used as a novel hydrogen-bond marker in such compounds.

Application of Laser-Induced Acoustic Desorption for Molecular Rotational Resonance Spectroscopy.

Molecular Rotational Resonance (MRR) spectroscopy is a uniquely precise tool for the determination of molecular structures of volatile compounds in mixtures, as the characteristic rotational transition frequencies of a molecule are extremely sensitive to its 3D structure through the moments of inertia in a three-dimensional coordinate system. This enables identification of the compounds based on just a few parameters that can be calculated, as opposed to, for example, mass spectrometric data, which often require expert analysis of 10-20 different signals and the use of many standards/model compounds. This paper introduces a new sampling technique for MRR, laser-induced acoustic desorption (LIAD), to allow the vaporization of nonvolatile and thermally labile analytes without the need for excessive heating or derivatization. In this proof-of-concept study, LIAD was successfully coupled to an MRR instrument to conduct measurements on seven compounds with differing polarities, molecular weights, and melting and boiling points. Identification of three isomers in a mixture was also successfully performed using LIAD/MRR. Based on these results, LIAD/MRR is demonstrated to provide a powerful approach for the identification of nonvolatile and/or thermally labile analytes with molecular weights up to 600 Da in simple mixtures, which does not require the use of reference compounds. In the future, applications to more complex mixtures, such as those relevant to pharmaceutical research, and quantitative aspects of LIAD/MRR will be reported.

Millimeter and Submillimeter Spectroscopy of the Deuterated Molecular Ion SD+

Seven rotational and fine-structure transitions of the deuterated molecular ion SD+ in the X 3Σ− ground electronic state have been measured in the 271–863 GHz region in the laboratory. This ion has been produced by direct-current glow discharge using a mixture of D2S and argon in a free space cell in a temperature range of −140°C to −160°C. The rotational, centrifugal distortion, spin–spin interaction, and hyperfine constants have been determined; the standard deviation of the residuals in the fitting is 109 kHz. The set of obtained spectroscopic parameters provides a list of accurate submillimeter rest frequencies of SD+ for astronomical detection. We have investigated lines of SD+ toward the quasar PKS 1830-211 using the Atacama Large Millimeter/submillimeter Array archive, as the z = 0.89 molecular absorber exists in front of this quasar. A data set covering the 297 GHz region includes the N J = 23–12 transition at 561 GHz due to redshift, providing an upper limit of the column density N tot = 3 × 1012 cm−2 for SD+.

Rotational Spectrum and First Interstellar Detection of 2-methoxyethanol Using ALMA Observations of NGC 6334I

We use both chirped-pulse Fourier transform and frequency-modulated absorption spectroscopy to study the rotational spectrum of 2-methoxyethanol (CH3OCH2CH2OH) in several frequency regions ranging from 8.7 to 500 GHz. The resulting rotational parameters permitted a search for this molecule in Atacama Large Millimeter/submillimeter Array (ALMA) observations toward the massive protocluster NGC 6334I, as well as source B of the low-mass protostellar system IRAS 16293−2422. A total of 25 rotational transitions are observed in the ALMA Band 4 data toward NGC 6334I, resulting in the first interstellar detection of 2-methoxyethanol. A column density of 1.3−0.9+1.4×1017 cm−2 is derived at an excitation temperature of 143−39+31 K. However, molecular signal is not observed in the Band 7 data toward IRAS 16293−2422B, and an upper-limit column density of 2.5 × 1015 cm−2 is determined. Various possible formation pathways—including radical recombination and insertion reactions—are discussed. We also investigate physical differences between the two interstellar sources that could result in the observed abundance variations.

Charting circumstellar chemistry of carbon-rich asymptotic giant branch stars

Context. Asymptotic giant branch (AGB) stars are major contributors to the chemical enrichment of the interstellar medium through nucleosynthesis and extensive mass loss. Direct measures of both processes can be obtained by studying their circumstellar envelopes in molecular line emission. Most of our current knowledge of circumstellar chemistry, in particular in a C-rich environment, is based on observations of the carbon star IRC +10216. Aims. We aim to obtain a more generalised understanding of the chemistry in C-rich AGB circumstellar envelopes by studying a sample of three carbon stars, IRAS 15194–5115, IRAS 15082–4808, and IRAS 07454–7112, and to observationally test the archetypal status often attributed to IRC +10216. Methods. We performed spatially resolved, unbiased spectral surveys in ALMA Band 3 (85–116 GHz). We estimated the sizes of the molecular emitting regions using azimuthally averaged radial profiles of the line brightness distributions. We derived abundance estimates, using a population diagram analysis for molecules with multiple detected lines, and using single-line analytical calculations for the others. Results. We identify a total of 132 rotational transitions from 49 molecular species. There are two main morphologies of the brightness distributions: centrally peaked (CS, SiO, SiS, HCN) and shell-like (CN, HNC, C2H, C3H, C4H, C3N, HC5N, c-C3H2). The brightness distributions of HC3N and SiC2 have both a central and a shell component. The qualitative behaviour of the brightness distributions of all detected molecules, in particular their relative locations with respect to the central star, is the same for all three stars, and consistent with those observed towards IRC +10216. Of the shell distributions, the cyanopolyynes peak at slightly smaller radii than the hydrocarbons, and CN and HNC show the most extended emission. The emitting regions for each species are the smallest for IRAS 07454–7112, consistent with this object having the lowest circumstellar density within our sample. We find that, within the uncertainties of the analysis, the three stars present similar abundances for most species, and also compared to IRC +10216. We find, tentatively, that SiO is more abundant in our three stars compared to IRC+10216, and that the hydrocarbons are under-abundant in IRAS 07454–7112 compared to the other stars and IRC +10216. Our estimated 12C/13C ratios match well the literature values for the three sources and our estimated silicon and sulphur isotopic ratios are very similar across the three stars and IRC +10216. Conclusions. The observed circumstellar chemistry appears very similar across our sample and compared to that of IRC +10216, both in terms of the relative location of the emitting regions and molecular abundances. This implies that, to a first approximation, the chemical models tailored to IRC +10216 are, at least, able to reproduce the observed chemistry in C-rich envelopes across roughly an order of magnitude in wind density.

Giant enhancement of high-order rotational and rovibrational transitions in near-field spectroscopy in proximity to nanostructures

Giant enhancement of high-order rotational and rovibrational transitions in near-field spectroscopy in proximity to nanostructures