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Context. The spectra of four low-lying vibrational states of both anti and gauche conformers of normal-propyl cyanide were previously measured and analyzed in two spectral windows between 36 and 127 GHz. All states were then identified in a spectral line survey called Exploring Molecular Complexity with ALMA (EMoCA) toward Sagittarius B2(N) between 84.1 and 114.4 GHz with the Atacama Large Millimeter/submillimeter Array (ALMA) in its Cycles 0 and 1. Aims. We wanted to extend the measurements and analysis up to 506 GHz to provide accurate predictions over a much wider range of frequencies, quantum numbers and energies. Methods. We carried out measurements in two additional frequency windows up to 506 GHz. Results. For the gauche conformer, a large number of both a- and b-type transitions were identified. For the anti conformer, transitions were predominantly, but not exclusively, a-type. We hence improved molecular parameters for the ground states of both anti- and gauche-n-propyl cyanide and for excited vibrational states of the gauche conformer (v30 = 1, v29 = 1, v30 = 2, v28 = 1) and anti conformer (v30 = 1, v18 = 1, v30 = 2, v29 = 1) with high order coupling parameters determined between v18 = 1 and v30 = 2. Parameters are published for the first time for v18 = v30 = 1 of the anti conformer and for v29 = v30 = 1 of the gauche conformer. Conclusions. In total 15385 lines have been incorporated in the fits and should allow good predictions for unperturbed lines over the whole operating range of radio-telescopes. Evidence is found for vibrational coupling for some levels above 380 GHz. The coupling between v18 = 1 and v30 = 2 of the anti conformer has been well characterized. An additional list of 740 lines showing potential but as yet unidentified coupling has been provided for astrophysical identification.

Methyl mercaptan (CH$_3$SH) is an important sulfur-bearing species in the interstellar medium, terrestrial environment, and potentially in planetary atmospheres. The aim of the present study is to provide accurate spectroscopic parameters for the most abundant minor isotopolog CH$_3$$^{34}$SH to support radio astronomical observations at millimeter and submillimeter wavelengths. The rotational spectrum of CH$_3$$^{34}$SH, which is complicated by the large-amplitude internal rotation of the CH$_3$ group versus the $^{34}$SH frame, was investigated in the 49$-$510 GHz and 1.1$-$1.5 THz frequency ranges in natural isotopic abundance. The analysis of the spectrum was performed up to the second excited torsional state, and the obtained data were modeled with the RAM36 program. A fit within experimental accuracy was obtained with a RAM Hamiltonian model that uses 72 parameters. Predictions based on this fit are used to search for CH$_3$$^{34}$SH with the Atacama Large Millimeter/submillimeter Array (ALMA) toward the hot molecular core Sgr B2(N2), but blends with emission lines of other species prevent its firm identification in this source., Comment: 8 pages, Astron. Astrophys., in press

We present a new global study of the millimeter (mm) wave, submillimeter (sub-mm) wave, and terahertz (THz) spectra of the lowest three torsional states of methyl mercaptan (CH$_3$SH). New measurements have been carried out between 50 and 510 GHz using the Kharkiv mm wave and the Cologne sub-mm wave spectrometers whereas THz spectra records were used from our previous study. The new data, involving torsion-rotation transitions with $J$ up to 61 and $K_a$ up to 18, were combined with previously published measurements and fit using the rho-axis-method torsion-rotation Hamiltonian. The final fit used 124 parameters to give an overall weighted root-mean-square deviation of 0.72 for the dataset consisting of 6965 microwave (MW) and 16345 far-infrared line frequencies sampling transitions within and between the ground, first, and second excited torsional states. This investigation presents a two-fold expansion in the $J$ quantum numbers and a significant improvement in the fit quality, especially for the MW part of the data, thus allowing us to provide more reliable predictions to support astronomical observations., Comment: 12 pages; Astron. Astrophys., in press

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We report the first gas-phase vibrational spectra of the hydrocarbon ions C3H+ and C3H2+. The ions were produced by electron impact ionization of allene. Vibrational spectra of the mass-selected ions tagged with Ne were recorded using infrared predissociation spectroscopy in a cryogenic ion trap instrument using the intense and widely tunable radiation of a free electron laser. Comparison of high-level quantum chemical calculations and resonant depletion measurements revealed that the C3H+ ion is exclusively formed in its most stable linear isomeric form, whereas two isomers were observed for C3H2+. Bands of the energetically favored cyclic c-C3H2+ are in excellent agreement with calculated anharmonic frequencies, whereas for the linear open-shell HCCCH+ (2Πg) a detailed theoretical description of the spectrum remains challenging because of Renner-Teller and spin-orbit interactions. Good agreement between theory and experiment, however, is observed for the frequencies of the stretching modes for which an anharmonic treatment was possible. In the case of linear l-C3H+, small but non-negligible effects of the attached Ne on the ion fundamental band positions and the overall spectrum were found.

Methyl mercaptan (CH3SH) is a known interstellar molecule with abundances high enough that the detection of some of its minor isotopologues is promising. The present study aims at providing accurate spectroscopic parameters for the (13)CH3SH isotopologue to facilitate its identification in the interstellar medium at millimetre and submillimetre wavelengths. Through careful analysis of recent CH3SH spectra from 49-510 GHz and 1.1-1.5 THz recorded at natural isotopic composition, extensive assignments were possible not only for the ground torsional state of (13)CH3SH, but also in the first and second excited states. The torsion-rotation spectrum displays complex structure due to the large-amplitude internal rotation of the (13)CH3 group, similar to the main and other minor isotopic species of methyl mercaptan. The assigned transition frequencies have been fitted to within experimental error with a 52-parameter model employing the RAM36 programme. With predictions based on this fit, (13)CH3SH was searched for in spectra from the Atacama Large Millimetre/submillimetre Array (ALMA) towards the Galactic centre source Sgr B2(N2). Several transitions were expected to be observable, but all of them turned out to be severely blended with emission from other species, which prevents us from identifying (13)CH3SH in this source., Comment: 20 pages (with figures and tables); Can. J. Phys. (https://www.nrcresearchpress.com/journal/cjp), accepted

Cyanamide is one of the few interstellar molecules containing two chemically different N atoms. It was detected recently toward the solar-type protostar IRAS 16293-2422 B together with H$_2$N$^{13}$CN and HDNCN in the course of the Atacama Large Millemeter/submillimeter Array (ALMA) Protostellar Interferometric Line Survey (PILS). The detection of the 15N isotopomers or the determination of upper limits to their column densities was hampered by the lack of accurate laboratory data at the frequencies of the survey. We wanted to determine spectroscopic parameters of the $^{15}$N isotopomers of cyanamide that are accurate enough for predictions well into the submillimeter region and to search for them in the PILS data. We investigated the laboratory rotational spectra of H$_2^{15}$NCN and H$_2$NC$^{15}$N in the selected region between 192 and 507~GHz employing a cyanamide sample in natural isotopic composition. Additionally, we recorded transitions of H$_2$N$^{13}$CN. We obtained new or improved spectroscopic parameters for the three isotopic species. Neither of the $^{15}$N isotopomers of cyanamide were detected unambiguously in the PILS data. Two relatively clean lines can be tentatively assigned to H$_2^{15}$NCN. If confirmed, their column densities would imply a low $^{14}$N/$^{15}$N ratio for cyanamide toward this source. The resulting line lists should be accurate enough for observations up to about 1 THz. More sensitive observations, potentially at different frequencies, may eventually lead to the astronomical detection of these isotopic species., Astron. Astrophys., 8 pages; paper appeared; CDMS links corrected

Molecular ions of phenol and aniline as well as the fragment ion at m/z 66 formed by electron ionization are examined with cryogenic messenger-IR ion spectroscopy and theory. According to the recorded IR spectra aromatic ground state molecular ions of phenol and aniline are clearly identified. Similar to earlier reports our new set of spectroscopic and computational results supports the assumption that tautomeric molecular ions of phenol and aniline are only short-lived intermediates in the reaction path to the ultimate CO loss reaction product of phenol as well as the HNC loss product of aniline. Even the present cryogenic messenger-IR ion spectroscopy approach failed to collect spectroscopic evidence of the intermediate presence of these elusive tautomers of phenol and aniline molecular ions. However, our study clearly shows that the electron ionization mass spectrometry dissociation product ion of phenol and aniline at m/z 66 is the cyclopentadiene radical cation [C5H6] + for the presence of which convincing spectroscopic evidence could be collected proving the structure assignment and identification. All messenger-IR ion spectroscopy experiments were conducted on a cryogenic 22-pole ion trap with the use of neon atoms for tagging. The MS instrument was coupled to a free electron laser delivering wavelength tunable IR radiation for spectroscopy. Harmonic and anharmonic force field calculations complement the experiments and support band assignments of the recorded IR spectra and general data interpretation.

The pure rotational spectrum of the CCl+ (X 1Σ+) cation has been observed for the first time using a cryogenic ion trap apparatus and applying an action spectroscopy scheme. The major isotopic species 12C35Cl+ was observed up to the J = 4 ← 3 transition around 191 GHz and 12C37Cl+ was observed up to J = 3 ← 2. All transitions exhibit (partially) resolved hyperfine structure from the presence of the chlorine nuclei (both I = 3/2). This study provides the data needed for future sensitive radio astronomical searches for CCl+ in space.

5 pags., 5 figs., 2 tabs., A cryogenic 22-pole ion trap apparatus is used in combination with a table-top pulsed IR source to probe weakly bound CH-He and CH-He complexes by predissociation spectroscopy at 4 K. The infrared photodissociation spectra of the C–H stretching vibrations are recorded in the range of 2720–2800 cm. The spectrum of CH-He exhibits perpendicular transitions of a near prolate top with a band origin at 2745.9 cm, and thus confirms it to have a T-shaped structure. For CH-He, the C-H stretch along the symmetry axis of this oblate top results in parallel transitions., This work has been supported via Collaborative Research Centre 956, sub-project B2, funded by the Deutsche Forschungsgemein- schaft (DFG, project ID 184018867) as well as DFG SCHL 341/15–1 (‘‘Cologne Center for Terahertz Spectroscopy”) and AS 319/2–2. JLD acknowledges partial financial support from the Agencia Estatal de Investigación (AEI) through grant FIS2016- 77726-C3-1-P and from the European Research Council through grant agreement ERC-2013-SyG-610256-NANOCOSMOS.

The high resolution vibrational spectrum of ethyl cyanide (C2H5CN) has been investigated in the far-IR using synchrotron-based Fourier transform spectroscopy. The assignment was performed using the Automated Spectral Assignment Procedure (ASAP) allowing accurate rotational energy levels of the four lowest fundamental vibrations of the species, namely the v 13 = 1 @ 205.934099(8) cm−1, v 21 = 1 @ 212.141101(8) cm−1, v 20 = 1 @ 372.635293(15) cm−1, and v 12 = 1 @ 532.699617(16) cm−1 states, to be determined. The analysis not only confirms the applicability of the ASAP in the treatment of (dense) high-resolution infrared spectra but also reveals some of its limitations. Complementary to the infrared study, the pure rotational spectrum of C2H5CN was also studied in selected frequency ranges from 75 to 255 GHz. New observations of a prototypical high-mass star-forming region, G327.3–0.6, performed with the Atacama Large Millimeter Array show that vibrational satellites of C2H5CN can be very intense, of order several tens of Kelvin in units of brightness temperature.

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 figures

H 3 + and two of its deuterated variants have been trapped and cooled in a 4 K trap machine, and their fundamental vibrational transitions probed with the laser induced reactions method. With the help of a frequency comb system the line centers are determined with high accuracy and precision, typically well below 1 MHz. For the deuterated variants, ground state combination differences allow for comparison with existing rotational THz data, and the accurate prediction thereof.

The ν 7 antisymmetric C–H stretching fundamental of c- C 3 H 2 + has been characterized in a cryogenic 22-pole ion trap by a novel type of action spectroscopy, in which the rovibrational excitation of c- C 3 H 2 + is detected as a slowing down of the low-temperature reaction c- C 3 H 2 + + H2 → C 3 H 3 + + H. Ninety-one rovibrational transitions with partly resolved fine structure doublets were measured in high resolution. Supported by high-level quantum chemical calculations, spectroscopic parameters were determined by fitting the observed lines with an effective Hamiltonian for an asymmetric rotor in a doublet electronic ground state, X ˜ A 1 2 , yielding a band origin at 3113.6400(3) cm−1. Based on these spectroscopic parameters, the rotational spectrum of this astronomically important molecule is predicted.

The jet-cooled rotational spectrum of 1,2-butanedithiol was observed in the frequency region 2–8 GHz. Two conformers were detected for the molecule, corresponding to anti- and gauche-carbon molecular skeletons, both featuring a gauche arrangement of the two thiol groups. All 13C and 34S monosubstituted isotopologues were additionally assigned in natural abundance for the most stable anti isomer, while only the two 34S species were detected for the weaker gauche conformation. The structural analysis included ground-state effective structures, isotopic substitution coordinates, B3LYP-D3(BJ) density functional molecular orbital calculations and non-covalent interactions mapping with NCIPlot. The structural data confirm that the two thiol groups synchronize their orientation either parallel or antiparallel to support intramolecular S–H⋯S weak hydrogen bonding, reminiscent of the intramolecular hydrogen bond networks observed in adjacent alcohol groups. DFT calculations on 1,2-butanediol and 1,2-ethanedithiol offered structural comparisons with the title compound.

Low frequency combination bands of

4 pags., 1 fig.; 2 tabs., We report rest frequencies for rotational transitions of the deuterated ammonium isotopologues NH3D+, NH2D2 +, and NHD3 +, measured in a cryogenic ion trap machine. For the symmetric tops NH3D+ and NHD3 +, one and three transitions are detected, respectively, and five transitions are detected for the asymmetric top NH2D2 +. While the lowest frequency transition of NH3D+ was already known in the laboratory and space, this work enables the future radio astronomical detection of the two other isotopologues., This work (including a research stay of J.L.D. in Köln) has been supported by the Deutsche Forschungsgemeinschaft (DFG) via SFB 956 project B2 and the Gerätezentrum “Cologne Center for Terahertz Spectroscopy.” J.L.D. acknowledges partial financial support from the Spanish MINECO through grant FIS2016-77726-C3-1-P and from the European Research Council through grant agreement ERC-2013-SyG- 610256-NANOCOSMOS.

The ground state of He–HCO+ is investigated using a recently developed double resonance technique, consisting of a rotational transition followed by a vibrational transition into a dissociative state. In order to derive precise predictions for the rotational states, the high resolution infrared predissociation spectroscopy of the v1 C–H stretching mode is revisited. Eleven pure rotational transitions are measured via the double resonance method. A least squares fit of these transitions to a standard linear rotor Hamiltonian reveals that the semirigid rotor model cannot fully describe the loosely bound He–HCO+ complex. The novel double resonance technique is compared with other action spectroscopic schemes, and some potential future applications are presented.

The long-searched C-H stretches of the fundamental ions CH+ and 13CH+ have been observed for the first time in the laboratory. For this, the state-dependent attachment of He atoms to these ions at cryogenic temperatures has been exploited to obtain high-resolution rovibrational data. In addition, the lowest rotational transitions of CH+, 13CH+ and CD+ have been revisited and their rest frequency values improved substantially.

A novel rotational spectroscopy method applicable to ions stored in cold traps is presented. In a double resonance scheme, rotational excitation is followed by vibrational excitation into a dissociative resonance. Its general applicability is demonstrated for the CH_{3}^{+}-He complex, which undergoes predissociation through its C-H stretching modes ν_{1} and ν_{3}. High resolution rotational transitions are recorded for this symmetric top, and small unexpected splittings are resolved for K=1. Advantages and potential future applications of this new approach are discussed.

The protonated oxygen molecule, O

5 pags., 2 figs., 5 tabs., C-H stretches of the fundamental ions CH and CH, which have long been searched for, have been observed for the first time in the laboratory. The state-dependent attachment of He atoms to these ions at cryogenic temperatures has been exploited to obtain high-resolution rovibrational data. In addition, the lowest rotational transitions of CH, CH and CD have been revisited and their rest frequency values have improved substantially., This work (including the research visit of J.L.D. to Köln) has been supported by the Deutsche Forschungsgemeinschaft (DFG) via SFB 956 project B2 and the Gerätezentrum “Cologne Center for Terahertz Spectroscopy.” J.L.D. acknowledges partial support from the Spanish MINECO through grant FIS2016-77726-C3-1-P and from the European Research Council through grant agreement ERC-2013-SyG-610256 NANOCOSMOS.

Thioformaldehyde is an abundant molecule in various regions of the interstellar medium. However, available laboratory data limit the accuracies of calculated transition frequencies in the submillimeter region, in particular for minor isotopic species. We aim to determine spectroscopic parameters of isotopologs of H2CS that are accurate enough for predictions well into the submillimeter region. We investigated the laboratory rotational spectra of numerous isotopic species in natural isotopic composition almost continuously between 110 and 377 GHz. Individual lines were studied for most species in two frequency regions between 566 and 930 GHz. Further data were obtained for the three most abundant species in the 1290-1390 GHz region. New or improved spectroscopic parameters were determined for seven isotopic species. Quantum-chemical calculations were carried out to evaluate the differences between ground state and equilibrium rotational parameters to derive semi-empirical equilibrium structural parameters. The spectroscopic parameters are accurate enough for predictions well above 1 THz with the exception of H2(13)C(34)S where the predictions should be reliable to around 700 GHz., Comment: Astron. Astrophys., in press; 12 pages

The fragment of the 1-methylpyrene cation, C17H11+, is expected to exist in two isomeric forms, 1-pyrenemethylium PyrCH2+ and the tropylium containing species PyrC7+ . We measured the infrared (IR) action spectrum of cold C17H11+ tagged with Ne using a cryogenic ion trap instrument coupled to the FELIX laser. Comparison of the experimental data with density functional theory calculations allows us to identify the PyrCH2+ isomer in our experiments. The IR Multi-Photon Dissociation spectrum was also recorded following the C2H2 loss channel. Its analysis suggests combined effects of anharmonicity and isomerisation while heating the trapped ions, as shown by molecular dynamics simulations., Chemical Physics Letters, Elsevier, In press

73 rd International Symposium on Molecular Spectroscopy. June 18-22, 2018 - Champaign-Urbana, Illinois (USA) -.http://isms.illinois.edu/2018/Archive.php

The rotational spectra of three mono-substituted deuterium isotopologues of the anti conformer of ethanol have been measured between 35 and 500 GHz. One of these, CH 2 DCH 2 OH, exists as two distinct conformers according to the position of the deuterium atom with respect to the molecular skeleton. The dataset was constrained for fitting with a standard Watson-S reduction Hamiltonian by rejecting transitions from high-lying states, which appear to be perturbed by the gauche states, and by averaging some small methyl torsional splits. This treatment is compatible with the one we employed for the 13 C containing isotopologues of ethanol, and with the needs for a first search for these species in the interstellar medium, in particular in spectra taken by ALMA. For this purpose an appropriate set of predictions is given.

Protonation of methane (CH 4 ), a rather rigid molecule well described by quantum mechanics, produces CH 5 + , a prototypical floppy molecule that has eluded definitive spectroscopic description. Experimental measurement of high-resolution spectra of pure CH 5 + samples poses a formidable challenge. By applying two types of action spectroscopy predicated on photoinduced reaction with CO 2 and photoinhibition of helium cluster growth, we obtained low-temperature, high-resolution spectra of mass-selected CH 5 + . On the basis of the very high accuracy of the line positions, we determined a spectrum of combination differences. Analysis of this spectrum enabled derivation of equally accurate ground state–level schemes of the corresponding nuclear spin isomers of CH 5 + , as well as tentative quantum number assignment of this enfant terrible of molecular spectroscopy.

Complexes of the triatomic hydrogen ion with helium were synthesised in a low-temperature 22-pole rf ion trap at He number densities of up to 1016 cm−3. Absolute ternary rate coefficients for sequentially attaching He atoms have been determined from the growth of complexes with increasing storage time. The number of helium-tagged ions is significantly reduced when increasing the nominal temperature from 4 to 25 K. Competition between attachment and dissociation via collisions leads to stationary Hen–H+3 (n up to 9) distributions. State-specific excitation of the trapped H+3 ions via IR transitions significantly reduces the formation of complexes. Tuning the laser to Δv2 = 1 transitions in the range of 2726 cm−1 leads to LIICG lines, i.e., to spectra caused by laser-induced inhibition of complex growth. In addition, almost 100 lines have been found between 2700 and 2765 cm−1, which are attributed to laser-induced dissociation of the in situ formed He–H+3 complex ions. These lines are not yet assigned; howe...

New millimeter-wave transitions of the CO–N 2 van der Waals complex have been observed using the intracavity OROTRON jet spectrometer in the frequency range of 103–159 GHz. For the less abundant form, CO– para N 2 , a total of 37 rotational transitions were assigned to three K = 0–0, 0–1, 2–1 subbands connecting the ( j CO , j N2 ) = (1, 1) and ( j CO , j N2 ) = (0, 1) internal rotor states. The upper K = 0 and K = 2 “stacks” of rotational levels were probed for the first time here by millimeter-wave spectroscopy following a recent infrared study by Rezaei et al. (2013). The observation of new subbands fixes with higher precision not only these upper K = 0 and K = 2 but also lower K = 1( f ) levels, not linked with other stacks in earlier rotational studies. For the more abundant form, CO– ortho N 2 , five new P -branch rotational transitions of the K = 0–0 “CO bending” subband are reported, thus extending previous measurements. Nuclear quadrupole hyperfine structure due to the presence of two equivalent 14 N nuclei was partly resolved and analyzed to give additional information about the angular orientation of the N 2 molecule in the complex.

The millimeter-wave spectrum of the cis conformer of disulfur dioxide, cis-OSSO, has been recorded in this study in the ranges 70–120 GHz and 340–500 GHz. Transitions of its second most abundant isotopologue, OS 34 SO , have also been observed. The species was produced in a radio frequency discharge through flowing SO 2 . An improved set of molecular parameters has been derived from the newly recorded data, allowing for accurate predictions throughout the millimeter-wave region and into the submillimeter-wave domain. Quantum-chemical calculations at the coupled-cluster level of theory have also been performed, providing an accurate set of structural parameters of this species for comparison with experimentally derived values.