arXiv subjects

Stephan Schlemmer

Publications and source records attributed to Stephan Schlemmer.

51 records · Page 3Linked to original sources

arXiv2019

Submillimeter spectroscopy and astronomical searches of vinyl mercaptan, C$_2$H$_3$SH

We have extended the pure rotational investigation of the two isomers syn and anti vinyl mercaptan to the millimeter domain using a frequency-multiplication spectrometer. The species were produced by a radiofrequency discharge in 1,2-ethanedithiol. Additional transitions have been re-measured in the centimeter band using Fourier-transform microwave spectroscopy to better determine rest frequencies of transitions with low-$J$ and low-$K_a$ values. Experimental investigations were supported by quantum chemical calculations on the energetics of both the [C$_2$,H$_4$,S] and [C$_2$,H$_4$,O] isomeric families. Interstellar searches for both syn and anti vinyl mercaptan as well as vinyl alcohol were performed in the EMoCA (Exploring Molecular Complexity with ALMA) spectral line survey carried out toward Sagittarius (Sgr) B2(N2) with the Atacama Large Millimeter/submillimeter Array (ALMA). Highly accurate experimental frequencies (to better than 100 kHz accuracy) for both syn and anti isomers of vinyl mercaptan have been measured up to 250 GHz; these deviate considerably from predictions based on extrapolation of previous microwave measurements. Reliable frequency predictions of the astronomically most interesting millimeter-wave lines for these two species can now be derived from the best-fit spectroscopic constants. From the energetic investigations, the four lowest singlet isomers of the [C$_2$,H$_4$,S] family are calculated to be nearly isoenergetic, which makes this family a fairly unique test bed for assessing possible reaction pathways. Upper limits for the column density of syn and anti vinyl mercaptan are derived toward the extremely molecule-rich star-forming region Sgr B2(N2) enabling comparison with selected complex organic molecules.

astro-ph.GA↗

arXiv2018

Accurate rotational rest frequencies for ammonium ion isotopologues

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.

astro-ph.GA↗

arXiv2018

100 GHz Room-Temperature Laboratory Emission Spectrometer

We present first results of a new heterodyne spectrometer dedicated to high-resolution spectroscopy of molecules of astrophysical importance. The spectrometer, based on a roomtemperature heterodyne receiver, is sensitive to frequencies between 75 and 110 GHz with an instantaneous bandwidth of currently 2.5 GHz in a single sideband. The system performance, in particular the sensitivity and stability, is evaluated. Proof of concept of this spectrometer is demonstrated by recording the emission spectrum of methyl cyanide, CH3CN. Compared to state-of-the-art radio telescope receivers the instrument is less sensitive by about one order of magnitude. Nevertheless, the capability for absolute intensity measurements can be exploited in various experiments, in particular for the interpretation of the ever richer spectra in the ALMA era. The ease of operation at room-temperature allows for long time integration, the fast response time for integration in chirped pulse instruments or for recording time dependent signals. Future prospects as well as limitations of the receiver for the spectroscopy of complex organic molecules (COMs) are discussed.

astro-ph.IM↗

arXiv2018

Identification of the fragment of the 1-methylpyrene cation by mid-IR spectroscopy

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.

physics.chem-ph↗

arXiv2018

First laboratory detection of vibration-rotation transitions of CH$^+$ and $^{13}$CH$^+$ and improved measurement of their rotational transition frequencies

The long-searched C-H stretches of the fundamental ions CH$^+$ and $^{13}$CH$^+$ 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$^+$, $^{13}$CH$^+$ and CD$^+$ have been revisited and their rest frequency values improved substantially.

astro-ph.GA↗

arXiv2017

Accurate frequency determination of vibration-rotation and rotational transitions of SiH+

The fundamental 28SiH+ ion has been characterized in a collaborative work, utilizing a hollow-cathode-discharge laser-spectrometer and a cryogenic ion trap spectrometer. Twenty-three vibration-rotation transitions around 4.75 um have been detected with high accuracy. This has facilitated the first direct measurement of the pure rotational transition J=1<-0 at 453056.3632(4) MHz in the trap spectrometer. The measured and accurately predicted transitions enable the search for this ion in space with IR and sub-mm telescopes.

astro-ph.GA↗

arXiv2017

Detection of interstellar ortho-D2H+ with SOFIA

We report on the detection of the ground-state rotational line of ortho-D2H+ at 1.477 THz (203 micron) using the German REceiver for Astronomy at Terahertz frequencies (GREAT) onboard the Stratospheric Observatory For Infrared Astronomy (SOFIA). The line is seen in absorption against far-infrared continuum from the protostellar binary IRAS 16293-2422 in Ophiuchus. The para-D2H+ line at 691.7 GHz was not detected with the APEX telescope toward this position. These D2H+ observations complement our previous detections of para-H2D+ and ortho-H2D+ using SOFIA and APEX. By modeling chemistry and radiative transfer in the dense core surrounding the protostars, we find that the ortho-D2H+ and para-H2D+ absorption features mainly originate in the cool (T<18 K) outer envelope of the core. In contrast, the ortho-H2D+ emission from the core is significantly absorbed by the ambient molecular cloud. Analyses of the combined D2H+ and H2D+ data result in an age estimate of ~500 000 yr for the core, with an uncertainty of ~200 000 yr. The core material has probably been pre-processed for another 500 000 years in conditions corresponding to those in the ambient molecular cloud. The inferred time scale is more than ten times the age of the embedded protobinary. The D2H+ and H2D+ ions have large and nearly equal total (ortho+para) fractional abundances of ~$10^{-9}$ in the outer envelope. This confirms the central role of H3+ in the deuterium chemistry in cool, dense gas, and adds support to the prediction of chemistry models that also D3+ should be abundant in these conditions.

astro-ph.GA↗

arXiv2016

Deuteration of ammonia in the starless core Ophiuchus/H-MM1

Ammonia and its deuterated isotopologues probe physical conditions in dense molecular cloud cores. With the aim of testing the current understanding of the spin-state chemistry of these molecules, we observed spectral lines of NH3, NH2D, NHD2, ND3, and N2D+ towards a dense, starless core in Ophiuchus with the APEX, GBT, and IRAM 30-m telescopes. The observations were interpreted using a gas-grain chemistry model combined with radiative transfer calculations. The chemistry model distinguishes between the different nuclear spin states of light hydrogen molecules, ammonia, and their deuterated forms. High deuterium fractionation ratios with NH2D/NH3=0.4, NHD2/NH2D=0.2, and ND3/NHD2=0.06 were found in the core. The observed ortho/para ratios of NH2D and NHD2 are close to the corresponding nuclear spin statistical weights. The chemistry model can approximately reproduce the observed abundances, but predicts uniformly too low ortho/para-NH2D, and too large ortho/para-NHD2 ratios. The longevity of N2H+ and NH3 in dense gas, which is prerequisite to their strong deuteration, can be attributed to the chemical inertia of N2 on grain surfaces. The discrepancies between the chemistry model and the observations are likely to be caused by the fact that the model assumes complete scrambling in principal gas-phase deuteration reactions of ammonia, which means that all the nuclei are mixed in reactive collisions. If, instead, these reactions occur through proton hop/hydrogen abstraction processes, statistical spin ratios are to be expected. The present results suggest that while the deuteration of ammonia changes with physical conditions and time, the nuclear spin ratios of ammonia isotopologues do not probe the evolutionary stage of a cloud.

astro-ph.GA↗

arXiv2016

Laboratory spectroscopic study and astronomical detection of vibrationally excited n-propyl cyanide

We performed 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. We determined line intensities of n-propyl cyanide in the ground vibrational states of its gauche and anti conformers toward the hot molecular core Sagittarius B2(N2) which suggest that we should also be able to detect transitions pertaining to excited vibrational states. We wanted to determine spectroscopic parameters of low-lying vibrational states of both conformers of n-propyl cyanide to search for them in our ALMA data. We recorded laboratory rotational spectra of n-propyl cyanide in two spectral windows between 36 and 127 GHz. We searched for emission lines produced by these states in the ALMA spectrum of Sagittarius B2(N2). We modeled their emission and the emission of the ground vibrational states assuming local thermodynamic equilibrium (LTE). We have made extensive assignments of a- and b-type transitions of the four lowest vibrational states of the gauche conformer which reach J and Ka quantum numbers of 65 and 20, respectively. We assigned mostly a-type transitions for the anti conformer with J and Ka quantum numbers up to 48 and 24, respectively. Rotational and Fermi perturbations between two anti states allowed us to determine their energy difference. The resulting spectroscopic parameters enabled us to identify transitions of all four vibrational states of each conformer in our ALMA data. The emission features of all states, including the ground vibrational state, are well-reproduced with the same LTE modeling parameters, which gives us confidence in the reliability of the identifications, even for the states with only one clearly detected line.

astro-ph.GA↗

arXiv2016

Laboratory rotational ground state transitions of NH$_3$D$^+$ 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.

astro-ph.IM↗

arXiv2016

High Resolution Laboratory Spectroscopy

In this short review we will highlight some of the recent advancements in the field of high-resolution laboratory spectroscopy that meet the needs dictated by the advent of highly sensitive and broadband telescopes like ALMA and SOFIA. Among these is the development of broadband techniques for the study of complex organic molecules, like fast scanning conventional absorption spectroscopy based on multiplier chains, chirped pulse instrumentation, or the use of synchrotron facilities. Of similar importance is the extension of the accessible frequency range to THz frequencies, where many light hydrides have their ground state rotational transitions. Another key experimental challenge is the production of sufficiently high number densities of refractory and transient species in the laboratory, where discharges have proven to be efficient sources that can also be coupled to molecular jets. For ionic molecular species sensitive action spectroscopic schemes have recently been developed to overcome some of the limitations of conventional absorption spectroscopy. Throughout this review examples demonstrating the strong interplay between laboratory and observational studies will be given.

astro-ph.IM↗

arXiv2016

The Cologne Database for Molecular Spectroscopy, CDMS, in the Virtual Atomic and Molecular Data Centre, VAMDC

The CDMS was founded 1998 to provide in its catalog section line lists of molecular species which may be observed in various astronomical sources using radio astronomy. The line lists contain transition frequencies with qualified accuracies, intensities, quantum numbers, as well as further auxilary information. They have been generated from critically evaluated experimental line lists, mostly from laboratory experiments, employing established Hamiltonian models. Seperate entries exist for different isotopic species and usually also for different vibrational states. As of December 2015, the number of entries is 792. They are available online as ascii tables with additional files documenting information on the entries. The Virtual Atomic and Molecular Data Centre was founded more than 5 years ago as a common platform for atomic and molecular data. This platform facilitates exchange not only between spectroscopic databases related to astrophysics or astrochemistry, but also with collisional and kinetic databases. A dedicated infrastructure was developed to provide a common data format in the various databases enabling queries to a large variety of databases on atomic and molecular data at once. For CDMS, the incorporation in VAMDC was combined with several modifications on the generation of CDMS catalog entries. Here we introduce related changes to the data structure and the data content in the CDMS. The new data scheme allows us to incorporate all previous data entries but in addition allows us also to include entries based on new theoretical descriptions. Moreover, the CDMS entries have been transferred into a mySQL database format. These developments within the VAMDC framework have been driven by the needs of the astronomical community to be able to deal efficiently with large data sets obtained with the Herschel Space Telescope or, more recently, with the Atacama Large Millimeter Array.

astro-ph.IM↗

arXiv2013

Dimethyl ether in its ground state, v=0, and lowest two torsionally excited states, v11=1 and v15=1, in the high-mass star-forming region G327.3-0.6

The goal of this paper is to determine the respective importance of solid state vs. gas phase reactions for the formation of dimethyl ether. This is done by a detailed analysis of the excitation properties of the ground state and the torsionally excited states, v11=1 and v15=1, toward the high-mass star-forming region G327.3-0.6. With the Atacama Pathfinder EXperiment 12 m submillimeter telescope, we performed a spectral line survey. The observed spectrum is modeled assuming local thermal equilibrium. CH3OCH3 has been detected in the ground state, and in the torsionally excited states v11=1 and v15=1, for which lines have been detected here for the first time. The emission is modeled with an isothermal source structure as well as with a non-uniform spherical structure. For non-uniform source models one abundance jump for dimethyl ether is sufficient to fit the emission, but two components are needed for the isothermal models. This suggests that dimethyl ether is present in an extended region of the envelope and traces a non-uniform density and temperature structure. Both types of models furthermore suggest that most dimethyl ether is present in gas that is warmer than 100 K, but a smaller fraction of 5%-28% is present at temperatures between 70 and 100 K. The dimethyl ether present in this cooler gas is likely formed in the solid state, while gas phase formation probably is dominant above 100 K. Finally, the v11=1 and v15=1 torsionally excited states are easily excited under the density and temperature conditions in G327.3-0.6 and will thus very likely be detectable in other hot cores as well.

astro-ph.GA↗

arXiv2010

Interstellar OH+, H2O+ and H3O+ along the sight-line to G10.6-0.4

We report the detection of absorption lines by the reactive ions OH+, H2O+ and H3O+ along the line of sight to the submillimeter continuum source G10.6$-$0.4 (W31C). We used the Herschel HIFI instrument in dual beam switch mode to observe the ground state rotational transitions of OH+ at 971 GHz, H2O+ at 1115 and 607 GHz, and H3O+ at 984 GHz. The resultant spectra show deep absorption over a broad velocity range that originates in the interstellar matter along the line of sight to G10.6$-$0.4 as well as in the molecular gas directly associated with that source. The OH+ spectrum reaches saturation over most velocities corresponding to the foreground gas, while the opacity of the H2O+ lines remains lower than 1 in the same velocity range, and the H3O+ line shows only weak absorption. For LSR velocities between 7 and 50 kms$^{-1}$ we estimate total column densities of $N$(OH+) $> 2.5 \times 10^{14}$ cm$^{-2}$, $N$(H2O+) $\sim 6 \times 10^{13}$ cm$^{-2}$ and $N$(H3O+) $\sim 4.0 \times 10^{13}$ cm$^{-2}$. These detections confirm the role of O$^+$ and OH$^+$ in initiating the oxygen chemistry in diffuse molecular gas and strengthen our understanding of the gas phase production of water. The high ratio of the OH+ by the H2O+ column density implies that these species predominantly trace low-density gas with a small fraction of hydrogen in molecular form.

astro-ph.GA↗

arXiv2007

Photodesorption of CO ice

At the high densities and low temperatures found in star forming regions, all molecules other than H2 should stick on dust grains on timescales shorter than the cloud lifetimes. Yet these clouds are detected in the millimeter lines of gaseous CO. At these temperatures, thermal desorption is negligible and hence a non-thermal desorption mechanism is necessary to maintain molecules in the gas phase. Here, the first laboratory study of the photodesorption of pure CO ice under ultra high vacuum is presented, which gives a desorption rate of 3E-3 CO molecules per UV (7-10.5 eV) photon at 15 K. This rate is factors of 1E2-1E5 larger than previously estimated and is comparable to estimates of other non-thermal desorption rates. The experiments constrains the mechanism to a single photon desorption process of ice surface molecules. The measured efficiency of this process shows that the role of CO photodesorption in preventing total removal of molecules in the gas has been underestimated.

astro-ph↗