arXiv subjects

Stephan Schlemmer

Publications and source records attributed to Stephan Schlemmer.

At least 37 records · Page 2Linked to original sources

arXiv2023

Rotational spectroscopy of the thioformaldehyde isotopologues H$_2$CS and H$_2$C$^{34}$S in four interacting excited vibrational states and an account on the rotational spectrum of thioketene, H$_2$CCS

An investigation of the rotational spectrum of the interstellar molecule thioformaldehyde between 110 and 377 GHz through a pyrolysis reaction revealed a multitude of absorption lines assignable to H$_2$CS and H$_2$C$^{34}$S in their lowest four excited vibrational states besides lines of numerous thioformaldehyde isotopologues in their ground vibrational states reported earlier as well as lines pertaining to several by-products. Additional transitions of H$_2$CS in its lowest four excited vibrational states were recorded in selected regions between 571 and 1386 GHz. Slight to strong Coriolis interactions occur between all four vibrational states with the exception of the two highest lying states because both are totally symmetric vibrations. We present combined analyses of the ground and the four interacting states for our rotational data of H$_2$CS and H$_2$C$^{34}$S. The H$_2$CS data were supplemented with two sets of high-resultion IR data in two separate analyses. The $v_2 = 1$ state has been included in analyses of Coriolis interactions of low-lying fundamental states of H$_2$CS for the first time and this improved the quality of the fits substantially. We extended furthermore assignments in $J$ of transition frequencies of thioketene in its ground vibrational state.

physics.chem-ph↗

arXiv2023

Rotational spectroscopy of oxirane-\textit{2,2}-$d_2$, $c$-CD$_2$CH$_2$O, and its tentative detection toward IRAS 16293$-$2422~B

We prepared a sample of oxirane doubly deuterated at one C atom and studied its rotational spectrum in the laboratory for the first time between 120~GHz and 1094~GHz. Accurate spectroscopic parameters up to eighth order were determined, and the calculated rest frequencies were used to identify $c$-CD$_2$CH$_2$O tentatively in the interstellar medium in the Atacama Large Millimeter/submillimeter Array Protostellar Interferometric Line Survey (PILS) of the Class 0 protostellar system IRAS 16293$-$2422. The $c$-CD$_2$CH$_2$O to $c$-C$_2$H$_4$O ratio was estimated to be $\sim$0.054 with $T_{\rm rot} = 125$ K. This value translates to a D-to-H ratio of $\sim$0.16 per H atom which is higher by a factor of 4.5 than the $\sim$0.036 per H atom obtained for $c$-C$_2$H$_3$DO. Such increase in the degree of deuteration referenced to one H atom in multiply deuterated isotopologs compared to their singly deuterated variants have been observed commonly in recent years.

astro-ph.GA↗

arXiv2022

Leak-out Spectroscopy, a universal method of action spectroscopy in cold ion traps

A novel method of spectroscopy in ion traps termed leak-out spectroscopy (LOS) is presented. Here, mass selected, cold ions are excited by an infrared laser. In a subsequent collision with a neutral buffer gas particle their internal energy is then transferred to kinetic energy. As a result, these ions leak out from the ion trap and are detected. The LOS scheme is generally applicable, very sensitive and close to background free when operated at low temperature. The potential of this method is demonstrated and characterized here for the first time by recording the rotationally resolved spectrum of the C-H stretching vibration $ν_1$ of linear C$_3$H$^+$. Besides performing high-resolution spectroscopy, this method opens up the way for analyzing the composition of trap content, e.g., determining isomer ratios, by selectively expelling isomers or other isobaric ions from the trap. Likewise, LOS can be used to prepare clean samples of structural and nuclear spin isomers.

physics.chem-ph↗

arXiv2022

Rotational spectroscopy of mono-deuterated oxirane ($c$-C$_2$H$_3$DO) and its detection towards IRAS 16293$-$2422 B

We prepared a sample of mono-deuterated oxirane and studied its rotational spectrum in the laboratory between 490 GHz and 1060 GHz in order to improve its spectroscopic parameters and consequently the calculated rest frequencies of its rotational transitions. The updated rest frequencies were employed to detect $c$-C$_2$H$_3$DO for the first time in the interstellar medium in the Atacama Large Millimetre/submillimetre Array (ALMA) Protostellar Interferometric Line Survey (PILS) of the Class 0 protostellar system IRAS 16293$-$2422. Fits of the detected lines using the rotation diagrams yield a temperature of $T_{\rm rot} = 103 \pm 19$ K, which in turn agrees well with 125 K derived for the $c$-C$_2$H$_4$O main isotopologue previously. The $c$-C$_2$H$_3$DO to $c$-C$_2$H$_4$O ratio is found to be $\sim$0.15 corresponding to a D-to-H ratio of $\sim$0.036 per H atom which is slightly higher than the D-to-H ratio of species such as methanol, formaldehyde, ketene and but lower than those of the larger complex organic species such as ethanol, methylformate and glycolaldehyde. This may reflect that oxirane is formed fairly early in the evolution of the prestellar cores. The identification of doubly deuterated oxirane isotopomers in the PILS data may be possible judged by the amount of mono-deuterated oxirane and the observed trend that multiply deuterated isotopologues have higher deuteration rates than their mono-deuterated variants.

astro-ph.GA↗

arXiv2022

LLWP -- A new Loomis-Wood Software at the Example of Acetone-13C1

Acetone-13C1 is a complex organic molecule with two internal methyl (-CH3) rotors having relatively low effective barriers to internal rotation of about 249 cm-1. This leads to two low-lying torsional modes and five internal rotation components resulting in a dense and complicated spectrum. In this study, measurements of acetone-13C1 were performed with an isotopically enriched sample in the frequency range 37-1102 GHz. Predicted spectra of acetone-13C1 created with ERHAM allow for future radio astronomical searches. Loomis-Wood plots are one approach to improve and fasten the analysis of such crowded spectra. In this study, the new Loomis-Wood software LLWP was used for fast and confident assignments. LLWP focuses on being user-friendly, intuitive, and applicable to a broad range of assignment tasks. The software is presented here and can be downloaded from llwp.astro.uni-koeln.de.

physics.chem-ph↗

arXiv2022

Rotational spectroscopy of isotopic oxirane, $c$-C$_2$H$_4$O

We studied the rotational spectrum of oxirane in a sample of natural isotopic composition in selected regions between 158 GHz and 1093 GHz. Investigations of the isotopologs with one $^{13}$C or one $^{18}$O were the primary focus in order to facilitate searches for them in space. We also examined the main isotopic species mainly to look into the performance of Watson's A and S reductions both in an oblate and in a prolate representation. Even though oxirane is a rather asymmetric oblate rotor, the A reduction in the III$^l$ representation did not yield a satisfactory fit, as was observed frequently earlier for other molecules. The other three combinations yielded satisfactory fits of similar quality among each other; the A reduction in the I$^r$ representation required two parameters less than both S reduction fits.

physics.chem-ph↗

arXiv2021

(Sub-)millimeter-wave spectroscopy of gauche-propanal

A detailed analysis of (sub-)millimeter-wave spectra of the vibrational ground state ($\upsilon=0$) combined with the energetically lowest excited vibrational state ($\upsilon_{24}=1$; aldehyde torsion) of gauche-propanal (g-C$_2$H$_5$CHO) up to 500 GHz is presented. Both vibrational states, $\upsilon=0$ and $\upsilon_{24}=1$, are treated with tunneling rotation interactions between their two respective tunneling states, which originate from two stable degenerate gauche-conformers; left- and right-handed configurations separated by a small potential barrier. Thanks to double-modulation double-resonance (DM-DR) measurements, important but weak $c$-type transitions connecting the tunneling states could be unambiguously assigned. In addition, Coriolis interaction as well as Fermi resonance between the two vibrational states needed to be taken into account to derive fits with experimental accuracy using Pickett's SPFIT program in a reduced axis system (RAS). Based on the rotational analysis, the fundamental vibrational frequency $ν_{24}$ of gauche-propanal is redetermined to 68.75037(30) cm$^{-1}$.

physics.chem-ph↗

arXiv2021

High-resolution infrared action spectroscopy of the fundamental vibrational band of CN+

Rotational-vibrational transitions of the fundamental vibrational modes of the $^{12}$C$^{14}$N$^+$ and $^{12}$C$^{15}$N$^+$ cations have been observed for the first time using a cryogenic ion trap apparatus with an action spectroscopy scheme. The lines P(3) to R(3) of $^{12}$C$^{14}$N$^+$ and R(1) to R(3) of $^{12}$C$^{15}$N$^+$ have been measured, limited by the trap temperature of approximately 4 K and the restricted tuning range of the infrared laser. Spectroscopic parameters are presented for both isotopologues, with band origins at 2000.7587(1) and 1970.321(1) cm$^{-1}$, respectively, as well as an isotope independent fit combining the new and the literature data.

physics.chem-ph↗

arXiv2021

Rovibrational spectroscopy of the CH$^+$-He and CH$^+$-He$_4$ complexes

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$_4$ 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$^{-1}$. The spectrum of CH$^+$-He exhibits perpendicular transitions of a near prolate top with a band origin at 2745.9 cm$^{-1}$, and thus confirms it to have a T-shaped structure. For CH$^+$-He$_4$, the C-H stretch along the symmetry axis of this oblate top results in parallel transitions.

physics.chem-ph↗

arXiv2021

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~$μ$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.

astro-ph.GA↗

arXiv2021

Rotational spectroscopy of isotopic cyclopropenone, $c$-H$_2$C$_3$O, and determination of its equilibrium structure

Cyclopropenone was first detected in the cold and less dense envelope of Sagittarius B2(N). It was found later in several cold dark clouds and it may be possible to detect its minor isotopic species in these environments. In addition, the main species may well be identified in warmer environments. We aim to extend existing line lists of isotopologs of c-H2C3O from the microwave to the millimeter region and create one for the singly deuterated isotopolog to facilitate their detections in space. Furthermore, we aim to extend the line list of the main isotopic species to the submillimeter region and to evaluate an equilibrium structure of the molecule. We employed a cyclopropenone sample in natural isotopic composition to investigate the rotational spectra of the main and 18O-containing isotopologs as well as the two isotopomers containing one 13C atom. Spectral recordings of the singly and doubly deuterated isotopic species were obtained using a cyclopropenone sample highly enriched in deuterium. We recorded rotational transitions in the 70-126 GHz and 160-245 GHz regions for all isotopologs and also in the 342-505 GHz range for the main species. Quantum-chemical calculations were carried out to evaluate initial spectroscopic parameters and the differences between ground-state and equilibrium rotational parameters in order to derive semi-empirical equilibrium structural parameters. We determined new or improved spectroscopic parameters for six isotopologs and structural parameters according to different structure models. The spectroscopic parameters are accurate enough to identify minor isotopic species at centimeter and millimeter wavelengths while those of the main species are deemed to be reliable up to 1 THz. Our structural parameters differ from earlier ones. The deviations are attributed to misassignments in the earlier spectrum of one isotopic species.

astro-ph.IM↗

arXiv2020

Efficient methanol production on the dark side of a prestellar core

We present ALMA maps of the starless molecular cloud core Ophiuchus/H-MM1 in the lines of deuterated ammonia (ortho-NH2D), methanol (CH3OH), and sulphur monoxide (SO). The dense core is seen in NH2D emission, whereas the CH3OH and SO distributions form a halo surrounding the core. Because methanol is formed on grain surfaces, its emission highlights regions where desorption from grains is particularly efficient. Methanol and sulphur monoxide are most abundant in a narrow zone that follows the eastern side of the core. This side is sheltered from the stronger external radiation field coming from the west. We show that photodissociation on the illuminated side can give rise to an asymmetric methanol distribution, but that the stark contrast observed in H-MM1 is hard to explain without assuming enhanced desorption on the shaded side. The region of the brightest emission has a wavy structure that rolls up at one end. This is the signature of Kelvin-Helmholtz instability occurring in sheared flows. We suggest that in this zone, methanol and sulphur are released as a result of grain-grain collisions induced by shear vorticity.

astro-ph.GA↗

arXiv2019

New laboratory techniques using heterodyne receivers

Two laboratory emission spectrometers have been designed and described previously. Here, we present a follow-up study with special focus on absolute intensity calibration of the new SURFER-spectrometer (SUbmillimeter Receiver For Emission spectroscopy of Rotational transitions), operational between 300 and 400~GHz and mostly coincident with ALMA (Atacama Large Millimeter/submillimeter Array) Band 7. Furthermore, we present a feasibility study to extend the detection frequencies up to 2~THz. First results have been obtained using the SOFIA (Stratospheric Observatory for IR Astronomy) upGREAT laboratory setup at the University of Cologne. Pure rotational spectra of the complex molecule vinyl cyanide have been obtained and are used to give an estimate on the sensitivity to record ro-vibrational transitions of molecules with astrophysical importance at 2~THz.

astro-ph.IM↗

arXiv2019

Laboratory rotational spectroscopy of isotopic acetone, CH$_3^{13}$C(O)CH$_3$ and $^{13}$CH$_3$C(O)CH$_3$, and astronomical search in Sagittarius B2(N2)

We want to study the rotational spectra of CH$_3^{13}$C(O)CH$_3$ and $^{13}$CH$_3$C(O)CH$_3$ and search for them in Sagittarius B2(N2). We investigated the laboratory rotational spectrum of isotopically enriched CH$_3^{13}$C(O)CH$_3$ between 40 GHz and 910 GHz and of acetone between 36 GHz and 910 GHz in order to study $^{13}$CH$_3$C(O)CH$_3$ in natural isotopic composition. In addition, we searched for emission lines produced by these species in a molecular line survey of Sagittarius B2(N) carried out with ALMA. Discrepancies between predictions of the main isotopic species and the ALMA spectrum prompted us to revisit the rotational spectrum of this isotopolog. We assigned 9711 new transitions of CH$_3^{13}$C(O)CH$_3$ and 63 new transitions of $^{13}$CH$_3$C(O)CH$_3$ in the laboratory spectra. More than 1000 additional lines were assigned for the main isotopic species. We modeled the ground state data of all three isotopologs satisfactorily with the ERHAM program. We find that models of the torsionally excited states $v _{12} = 1$ and $v _{17} = 1$ of CH$_3$C(O)CH$_3$ improve only marginally. No transition of CH$_3^{13}$C(O)CH$_3$ is clearly detected toward the hot molecular core Sgr B2(N2). However, we report a tentative detection of $^{13}$CH$_3$C(O)CH$_3$ with a $^{12}$C/$^{13}$C isotopic ratio of 27 that is consistent with the ratio previously measured for alcohols in this source. Several dozens of transitions of both torsional states of the main isotopolog are detected as well. Our predictions of CH$_3^{13}$C(O)CH$_3$ and CH$_3$C(O)CH$_3$ are reliable into the terahertz region. The spectrum of $^{13}$CH$_3$C(O)CH$_3$ should be revisited in the laboratory with an enriched sample. Transitions pertaining to the torsionally excited states $v _{12} = 1$ and $v _{17} = 1$ of CH$_3$C(O)CH$_3$ could be identified unambiguously in Sagittarius B2(N2).

astro-ph.GA↗

arXiv2019

Rotational spectroscopy of isotopic species of methyl mercaptan at millimeter and submillimeter wavelengths: CH$_3$$^{34}$SH

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.

astro-ph.SR↗

arXiv2019

Rotational spectroscopy, dipole moment and $^{14}$N nuclear hyperfine structure of $iso$-propyl cyanide

Rotational transitions of $iso$-propyl cyanide, (CH$_3$)$_2$CHCN, also known as $iso$-butyronitrile, were recorded using long-path absorption spectroscopy in selected regions between 37 and 600 GHz. Further measurements were carried out between 6 and 20 GHz employing Fourier transform microwave (FTMW) spectroscopy on a pulsed molecular supersonic jet. The observed transitions reach $J$ and $K_a$ quantum numbers of 103 and 59, respectively, and yield accurate rotational constants as well as distortion parameters up to eighth order. The $^{14}$N nuclear hyperfine splitting was resolved in particular by FTMW spectroscopy yielding spin-rotation parameters as well as very accurate quadrupole coupling terms. In addition, Stark effect measurements were carried out in the microwave region to obtain a largely revised $c$-dipole moment component and to improve the $a$-component. The hyperfine coupling and dipole moment values are compared with values for related molecules both from experiment and from quantum chemical calculations.

astro-ph.IM↗

arXiv2019

Millimeter and Submillimeter Wave Spectroscopy of Propanal

The rotational spectra of the two stable conformers syn- and gauche-propanal (CH$_3$CH$_2$CHO) were studied in the millimeter and submillimeter wave regions from 75 to 500 GHz with the Cologne (Sub-)Millimeter wave Spectrometer. Furthermore, the first excited states associated with the aldehyde torsion and with the methyl torsion, respectively, of the $syn$-conformer were analyzed. The newly obtained spectroscopic parameters yield better predictions, thus fulfill sensitivity and resolution requirements in new astronomical observations in order to unambiguously assign pure rotational transitions of propanal. This is demonstrated on a radio astronomical spectrum from the Atacama Large Millimeter/submillimeter Array Protostellar Interferometric Line Survey (ALMA-PILS). In particular, an accurate description of observed splittings, caused by internal rotation of the methyl group in the $syn$-conformer and by tunneling rotation interaction from two stable degenerate $gauche$-conformers, is reported. The rotational spectrum of propanal is of additional interest because of its two large amplitude motions pertaining to the methyl and the aldehyde group, respectively.

astro-ph.SR↗

arXiv2019

Deuterated methyl mercaptan (CH$_3$SD): Laboratory rotational spectroscopy and search toward IRAS 16293-2422 B

Methyl mercaptan (also known as methanethiol), CH3SH, has been found in the warm and dense parts of high -- as well as low -- mass star-forming regions. The aim of the present study is to obtain accurate spectroscopic parameters of the S-deuterated methyl mercaptan CH$_3$SD to facilitate astronomical observations by radio telescope arrays at (sub)millimeter wavelengths. We have measured the rotational spectrum associated with the large-amplitude internal rotation of the methyl group of methyl mercaptan using an isotopically enriched sample in the 150-510 GHz frequency range using the Köln millimeter wave spectrometer. The analysis of the spectra has been performed up to the second excited torsional state. We present modeling results of these data with the RAM36 program. CH$_3$SD was searched for, but not detected, in data from the Atacama Large Millimeter/submillimeter Array (ALMA) Protostellar Interferometric Line Survey (PILS) of the deeply embedded protostar IRAS 16293-2422. The derived upper limit corresponds to a degree of deuteration of at most ~18%.

astro-ph.SR↗