Laboratory rotational ground state transitions of NH3_3D+^+ and CF+^+

Aims. This paper reports accurate laboratory frequencies of the rotational ground state transitions of two astronomically relevant molecular ions, NH3D+ and CF+. Methods. Spectra in the millimeter-wave band were recorded by the method of rotational state-selective attachment of He-atoms to the molecular ions stored and cooled in a cryogenic ion trap held at 4 K. The lowest rotational transition in the A state (ortho state) of NH$_3$D$^+$ ($J_K = 1_0 - 0_0$), and the two hyperfine components of the ground state transition of CF$^+$($J = 1 - 0$) were measured with a relative precision better than $10^{-7}$. Results. For both target ions the experimental transition frequencies agree with recent observations of the same lines in different astronomical environments. In the case of NH$_3$D$^+$ the high-accuracy laboratory measurements lend support to its tentative identification in the interstellar medium. For CF$^+$ the experimentally determined hyperfine splitting confirms previous quantum-chemical calculations and the intrinsic spectroscopic nature of a double-peaked line profile observed in the $J = 1 - 0$ transition towards the Horsehead PDR.Comment: 7 pages, 2 figure

Infrared predissociation spectroscopy of the hydrocarbon cations C3H+, C2H+, and C3H2+

Reactive hydrocarbon cations play an important role in the astrochemistry of the interstellar medium, but spectroscopic data, needed for their identification in astronomical observations, is sparse. Here we report the first gas-phase vibrational spectra of the linear C$_3$H$^+$ ($^1 \Sigma$), the radical cation C$_2$H$^+$ ($^3 \Pi$), and the linear-/cyclic-C$_3$H$_2^+$ ($^2 \Pi$ /$^2$A$_1$, resp.). Broadband spectra were recorded by Ne- and He-messenger infrared-predissociation (IR-PD) action spectroscopy in a cryogenic ($4-11$~K) ion trap instrument (FELion) in the $250-3500$~{\wn} range using a free electron laser and a MIR-OPO at the FELIX (Free-Electron Laser for Infrared eXperiments) laboratory. The band positions (determined with a precision of $1-2$~\wn) covering the C-H and C-C stretching as well as several bending modes are compared to high-level (CCSD(T) with large basis sets) quantum-chemical calculations with an emphasis on anharmonic effects and on the influence of the rare-gas messenger atom. The experimental and theoretical data provide a solid basis for subsequent IR high-resolution studies, with the ultimate goal to predict and measure accurate rotational spectra for a radio-astronomical search of these molecular ions in space

VIBRATIONAL AND ROTATIONAL SPECTROSCOPY IN CRYOGENIC ION TRAPS

Reactive molecular ions play a central role in the chemistry of the interstellar medium and in planetary atmospheres. Spectroscopic studies of these often elusive ions yield fundamental insights on their geometrical and electronic structure, and provide vibrational and rotational signatures needed for their identification in space. Cryogenic ion traps have proven to be ideal tools for the development of sensitive spectroscopic schemes of mass-selected, cold, and isolated molecular ions. Recent progress on these so-called action spectroscopic methods allows not only to probe electronic and vibrational excitation processes, but also to record high-resolution purely rotational molecular spectra\footnote{ S. Br\"{u}nken, L. Kluge, A. Stoffels, O. Asvany, and S. Schlemmer, Astrophys. J. Lett., 783, L4 (2014); A. Stoffels, L. Kluge, S. Schlemmer, and S. Br\"{u}nken, A\&A 593, A56 (2016); S. Br\"{u}nken, L. Kluge, A. Stoffels, J. Pèrez-Rios, and S. Schlemmer, J. Mol. Spectrosc., 332, 67 (2017)}, which are a direct prerequisite for radio-astronomical detections of new species in space as will be demonstrated with selected examples. In addition, details of broadband infrared experiments on several astrophysically important hydrocarbon cations ranging in size from comparatively small systems (e.g., C$_2$H$^+$, C$_3$H$_2^+$, and C$_3$H$^+$) to PAH cations will be given, using the unique combination of a cryogenic ion trap instrument\footnote{ O. Asvany, S. B\"{u}nken, L. Kluge, and S. Schlemmer, Appl. Phys. B, 114, 203 (2014)} interfaced to the free electron lasers at the FELIX Laboratory

Infrared action spectroscopy as tool for probing gas-phase dynamics: Protonated Dimethyl Ether, (CH3_3)2_2OH+^+, formed by the reaction of CH3_3OH2+_{2}^{+} with CH3_3OH

Methanol is one of the most abundant interstellar Complex Organic Molecules (iCOMs) and it represents a major building block for the synthesis of increasingly complex oxygen-containing molecules. The reaction between protonated methanol and its neutral counterpart, giving protonated dimethyl ether, (CH$_3$)$_2$OH$^+$, along with the ejection of a water molecule, has been proposed as a key reaction in the synthesis of dimethyl ether in space. Here, gas phase vibrational spectra of the (CH$_3$)$_2$OH$^+$ reaction product and of the [C$_2$H$_9$O$_2$]$^+$ intermediate complex(es), formed under different pressure and temperature conditions, are presented. The widely tunable free electron laser for infrared experiments, FELIX, was employed to record their vibrational fingerprint spectra using different types of infrared action spectroscopy in the $600-1700$ cm$^{-1}$ frequency range, complemented with measurements using an OPO/OPA system to cover the O-H stretching region $3400-3700$ cm$^{-1}$. The formation of protonated dimethyl ether as a product of the reaction is spectroscopically confirmed, providing the first gas-phase vibrational spectrum of this potentially relevant astrochemical ion.Comment: 15 pages, 6 figures, Molecular Physics, Published online: 22 Jun 2023, for associated data files see Zenodo repository at https://doi.org/10.5281/zenodo.786855

Infrared action spectroscopy of doubly charged PAHs and their contribution to the aromatic infrared bands

The so-called aromatic infrared bands are attributed to emission of polycyclic aromatic hydrocarbons. The observed variations toward different regions in space are believed to be caused by contributions of different classes of PAH molecules, i.e. with respect to their size, structure, and charge state. Laboratory spectra of members of these classes are needed to compare them to observations and to benchmark quantum-chemically computed spectra of these species. In this paper we present the experimental infrared spectra of three different PAH dications, naphthalene$^{2+}$, anthracene$^{2+}$, and phenanthrene$^{2+}$, in the vibrational fingerprint region 500-1700~cm$^{-1}$. The dications were produced by electron impact ionization of the vapors with 70 eV electrons, and they remained stable against dissociation and Coulomb explosion. The vibrational spectra were obtained by IR predissociation of the PAH$^{2+}$ complexed with neon in a 22-pole cryogenic ion trap setup coupled to a free-electron infrared laser at the Free-Electron Lasers for Infrared eXperiments (FELIX) Laboratory. We performed anharmonic density-functional theory calculations for both singly and doubly charged states of the three molecules. The experimental band positions showed excellent agreement with the calculated band positions of the singlet electronic ground state for all three doubly charged species, indicating its higher stability over the triplet state. The presence of several strong combination bands and additional weaker features in the recorded spectra, especially in the 10-15~$\mu$m region of the mid-IR spectrum, required anharmonic calculations to understand their effects on the total integrated intensity for the different charge states. These measurements, in tandem with theoretical calculations, will help in the identification of this specific class of doubly-charged PAHs as carriers of AIBs.Comment: Accepted for publication in A&

Detection of Vibrationally Excited CO in IRC+10216

Using the Submillimeter Array we have detected the J=3-2 and 2-1 rotational transitions from within the first vibrationally excited state of CO toward the extreme carbon star IRC+10216 (CW Leo). The emission remains spatially unresolved with an angular resolution of ~2" and, given that the lines originate from energy levels that are ~3100 K above the ground state, almost certainly originates from a much smaller (~10^{14} cm) sized region close to the stellar photosphere. Thermal excitation of the lines requires a gas density of ~10^{9} cm^{-3}, about an order of magnitude higher than the expected gas density based previous infrared observations and models of the inner dust shell of IRC+10216.Comment: Accepted for publication in ApJ Letter

Submillimeter narrow emission lines from the inner envelope of IRC+10216

A spectral-line survey of IRC+10216 in the 345 GHz band has been undertaken with the Submillimeter Array. Although not yet completed, it has already yielded a fairly large sample of narrow molecular emission lines with line-widths indicating expansion velocities of ~4 km/s, less than 3 times the well-known value of the terminal expansion velocity (14.5 km/s) of the outer envelope. Five of these narrow lines have now been identified as rotational transitions in vibrationally excited states of previously detected molecules: the v=1, J=17--16 and J=19--18 lines of Si34S and 29SiS and the v=2, J=7--6 line of CS. Maps of these lines show that the emission is confined to a region within ~60 AU of the star, indicating that the narrow-line emission is probing the region of dust-formation where the stellar wind is still being accelerated.Comment: 5 pages, 5 figures, Accepted for publication in Ap

PDRs4All IV. An embarrassment of riches: Aromatic infrared bands in the Orion Bar

(Abridged) Mid-infrared observations of photodissociation regions (PDRs) are dominated by strong emission features called aromatic infrared bands (AIBs). The most prominent AIBs are found at 3.3, 6.2, 7.7, 8.6, and 11.2 $\mu$m. The most sensitive, highest-resolution infrared spectral imaging data ever taken of the prototypical PDR, the Orion Bar, have been captured by JWST. We provide an inventory of the AIBs found in the Orion Bar, along with mid-IR template spectra from five distinct regions in the Bar: the molecular PDR, the atomic PDR, and the HII region. We use JWST NIRSpec IFU and MIRI MRS observations of the Orion Bar from the JWST Early Release Science Program, PDRs4All (ID: 1288). We extract five template spectra to represent the morphology and environment of the Orion Bar PDR. The superb sensitivity and the spectral and spatial resolution of these JWST observations reveal many details of the AIB emission and enable an improved characterization of their detailed profile shapes and sub-components. While the spectra are dominated by the well-known AIBs at 3.3, 6.2, 7.7, 8.6, 11.2, and 12.7 $\mu$m, a wealth of weaker features and sub-components are present. We report trends in the widths and relative strengths of AIBs across the five template spectra. These trends yield valuable insight into the photochemical evolution of PAHs, such as the evolution responsible for the shift of 11.2 $\mu$m AIB emission from class B$_{11.2}$ in the molecular PDR to class A$_{11.2}$ in the PDR surface layers. This photochemical evolution is driven by the increased importance of FUV processing in the PDR surface layers, resulting in a "weeding out" of the weakest links of the PAH family in these layers. For now, these JWST observations are consistent with a model in which the underlying PAH family is composed of a few species: the so-called 'grandPAHs'.Comment: 25 pages, 10 figures, to appear in A&

PDRs4All II: JWST's NIR and MIR imaging view of the Orion Nebula

The JWST has captured the most detailed and sharpest infrared images ever taken of the inner region of the Orion Nebula, the nearest massive star formation region, and a prototypical highly irradiated dense photo-dissociation region (PDR). We investigate the fundamental interaction of far-ultraviolet photons with molecular clouds. The transitions across the ionization front (IF), dissociation front (DF), and the molecular cloud are studied at high-angular resolution. These transitions are relevant to understanding the effects of radiative feedback from massive stars and the dominant physical and chemical processes that lead to the IR emission that JWST will detect in many Galactic and extragalactic environments. Due to the proximity of the Orion Nebula and the unprecedented angular resolution of JWST, these data reveal that the molecular cloud borders are hyper structured at small angular scales of 0.1-1" (0.0002-0.002 pc or 40-400 au at 414 pc). A diverse set of features are observed such as ridges, waves, globules and photoevaporated protoplanetary disks. At the PDR atomic to molecular transition, several bright features are detected that are associated with the highly irradiated surroundings of the dense molecular condensations and embedded young star. Toward the Orion Bar PDR, a highly sculpted interface is detected with sharp edges and density increases near the IF and DF. This was predicted by previous modeling studies, but the fronts were unresolved in most tracers. A complex, structured, and folded DF surface was traced by the H2 lines. This dataset was used to revisit the commonly adopted 2D PDR structure of the Orion Bar. JWST provides us with a complete view of the PDR, all the way from the PDR edge to the substructured dense region, and this allowed us to determine, in detail, where the emission of the atomic and molecular lines, aromatic bands, and dust originate