Vibrational and rotational spectroscopy of CD2H+

The lowest rotational levels ($J$=0-5) of the CD$_2$H$^+$ ground state have been probed by high-resolution rovibrational and pure rotational spectroscopy in a cryogenic 22-pole ion trap. For this, the $\nu_1$ rovibrational band has been revisited\footnote{M.-F. Jagod et al, J. Molec. Spectrosc. 153, 666, 1992}, detecting 107 transitions, among which 35 are new. The use of a frequency comb system allowed to measure the rovibrational transitions with high precision and accuracy, typically better than 1~MHz. The high precision has been confirmed by comparing combination differences in the ground and vibrationally excited state. For the ground state, this allowed for equally precise predictions of pure rotational transitions, 24 of which have been measured directly by a novel IR - mm-wave double resonance method\footnote{S. G\"artner et al, J. Phys. Chem. A 117, 9975, 2013}

Vibrational spectroscopy of H2He+ and D2He+

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Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X 2Σ+), with Unsaturated Hydrocarbons

Crossed molecular beam experiments of cyano radicals, CN(X 2Σ+, ν = 0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X 1Σ), ethylene, C2H4(X 1Ag), methylacetylene, CH3CCH(X 1A1), allene, H2CCCH2(X 1A1), dimethylacetylene, CH3CCCH3(X 1A1'), and benzene, C6H6 (X 1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X 1Σ+), vinylcyanide, C2H3CN (X 1A'), 1-methylcyanoacetylene, CH3CCCN (X 1A1), cyanoallene, H2CCCH(CN) (X 1A'), 3-methylcyanoacetylene, HCCCH2CN(X 1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X 1A'), and cyanobenzene, C6H5CN (X 1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X 1Σ+), and vinylcyanide, C2H3CN (X 1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed; since CH3CCH is the common precursor to H2CCCH(CN)/CH3CCCN and the latter isomer has been assigned unambiguously toward TMC-1 and OMC-1, H2CCCH(CN) is strongly expected to be present in both clouds as well. The formation of isonitrile isomers was not observed in our experiments. Since all reactions to HCCNC, C2H3NC, CH3CCNC, H2CCCH(NC), H2CCC(NC)(CH3), and C6H5NC are either endothermic or the exit barrier is well above the energy of the reactants, neutral-neutral reactions of cyano radicals with closed shell unsaturated hydrocarbons cannot synthesize isonitriles in cold molecular clouds. However, in outflow of carbon stars, the enhanced translational energy of both reactants close to the photosphere of the central star can compensate this endothermicity, and isonitriles might be formed in these hotter environments as well

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 mu m) using the German REceiver for Astronomy at Terahertz frequencies (GREAT) on. board 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 similar to 5. x. 10(5) yr for the core, with an uncertainty of similar to 2. x. 10(5) yr. The core material has probably been pre-processed for another 5. x. 10(5) years in conditions corresponding to those in the ambient molecular cloud. The inferred timescale is more than 10 times the age of the embedded protobinary. The D2H+ and H2D+ ions have large and nearly equal total (ortho+ para) fractional abundances of similar to 10(-9) in the outer envelope. This confirms the central role of H-3 + in the deuterium chemistry in cool, dense gas, and adds support to the prediction of chemistry models that also D-3(+) should be abundant in these conditions.Peer reviewe

Experiments with Ions and Clusters in a variable temperature 22-pole ion trap

In this work, 22-pole ion trap machines have been applied to investigate protonated water clusters H+(H2O)n (n=4..10) and ionic hydrocarbons CHn+ (n=2..5) at low temperatures. Protonated water clusters H+(H2O)n play an important role in atmospheric chemistry and in interstellar space. The Taipei 22-pole ion trap machine has been applied to kinetic and spectroscopic investigations of these clusters produced from a supersonic expansion in a corona discharge source. Using low-pressure He buffer gas for collisional thermalization, refrigeration of the ion trap by liquid nitrogen allows a good control of the cluster temperature over the range 80K-350K. This method provides an accurate means of determining the dissociation energies of the cluster ions by measuring their dissociation rates as a function of temperature and calculating their internal energies from vibrational frequencies provided by density functional theory. Results of the thermochemical measurements at well-defined cluster temperatures have been given for H+(H2O)n, n=4..10. The feasibility of using the ion trap to acquire temperature-dependent infrared spectra is presented. The deuteration and abstraction reactions of small ionic hydrocarbons CHn+ (n=2..5) with H2, HD and D2 and the subsequent association processes have been explored at temperatures down to 15K in the Chemnitz 22-pole apparatus. The reactions of the investigated ionic species and their isotopic variants are important for understanding ion-molecule processes in the interstellar medium. One of the starting points of the research program was the question whether protonated methane, CH5+, is subject to H-D-exchange in collisions with HD at low temperatures. It turns out that the rate coefficient for this deuteration process is very small, whereas CH3+ deuterates with HD by three subsequent fast exchange reactions to CD3+ at a temperature of 15K. The latter process is very efficient and happens close to the collision limit. The methane cation, CH4+, on the other hand, shows also some interesting features in collisions with H2, HD and D2. It exhibits an inverse temperature dependence with the rate coefficient increasing at least one order of magnitude going from 300K to 15K. Furthermore, reacting with HD at the temperature of 15K, the reaction channel leading to CH5+ is preferred over the D-atom abstraction channel (isotope effect).Im Rahmen dieser Arbeit wurden zwei Apparaturen mit 22-Pol-Ionenfallen benutzt, um protonierte Wassercluster H+(H2O)n (n=4..10) und kleine ionische Kohlenwasserstoffe CHn+ (n=2..5) bei tiefen Temperaturen zu untersuchen. Die in einer Koronaentladungsquelle erzeugten Cluster H+(H2O)n wurden kinetisch und spektroskopisch untersucht. Dazu wurden sie in einem 22-Pol-Speicher mithilfe eines He-Puffergases auf einer Temperatur zwischen 80K und 350K thermalisiert. Die Bestimmung der Bindungsenergien fuer Cluster der Groesse n=4..10 wird ermoeglicht durch die Messung der temperaturabhaengigen Dissoziationsraten und durch die Ermittlung der inneren Energien mittels berechneter Schwingungsfrequenzen. Temperaturabhaengige IR-Spektren im Bereich der freien OH-Streckschwingung wurden aufgenommen. Die Austausch- und Abstreifreaktionen von ionischen Kohlenwasserstoffen CHn+ (n=2..5) mit H2, HD und D2 und die darauffolgenden Assoziationsprozesse wurden im Temperaturbereich 15K bis 300K untersucht. Es stellt sich z.B. heraus, dass der H-D-Austauschprozess zwischen CH5+ und HD bei 15K sehr langsam ist, wogegen CH3+ mit jeder Kollision einen Austausch ausfuehrt. In der Abstreifreaktion von CH4+ mit Wasserstoffmolekuelen beobachtet man eine inverse Temperaturabhaengigkeit. Dies wird vorlaeufig mit einer laengeren Komplexlebensdauer bei tiefen Temperaturen erklaert

Experiments with Ions and Clusters in a variable temperature 22-pole ion trap

In this work, 22-pole ion trap machines have been applied to investigate protonated water clusters H+(H2O)n (n=4..10) and ionic hydrocarbons CHn+ (n=2..5) at low temperatures. Protonated water clusters H+(H2O)n play an important role in atmospheric chemistry and in interstellar space. The Taipei 22-pole ion trap machine has been applied to kinetic and spectroscopic investigations of these clusters produced from a supersonic expansion in a corona discharge source. Using low-pressure He buffer gas for collisional thermalization, refrigeration of the ion trap by liquid nitrogen allows a good control of the cluster temperature over the range 80K-350K. This method provides an accurate means of determining the dissociation energies of the cluster ions by measuring their dissociation rates as a function of temperature and calculating their internal energies from vibrational frequencies provided by density functional theory. Results of the thermochemical measurements at well-defined cluster temperatures have been given for H+(H2O)n, n=4..10. The feasibility of using the ion trap to acquire temperature-dependent infrared spectra is presented. The deuteration and abstraction reactions of small ionic hydrocarbons CHn+ (n=2..5) with H2, HD and D2 and the subsequent association processes have been explored at temperatures down to 15K in the Chemnitz 22-pole apparatus. The reactions of the investigated ionic species and their isotopic variants are important for understanding ion-molecule processes in the interstellar medium. One of the starting points of the research program was the question whether protonated methane, CH5+, is subject to H-D-exchange in collisions with HD at low temperatures. It turns out that the rate coefficient for this deuteration process is very small, whereas CH3+ deuterates with HD by three subsequent fast exchange reactions to CD3+ at a temperature of 15K. The latter process is very efficient and happens close to the collision limit. The methane cation, CH4+, on the other hand, shows also some interesting features in collisions with H2, HD and D2. It exhibits an inverse temperature dependence with the rate coefficient increasing at least one order of magnitude going from 300K to 15K. Furthermore, reacting with HD at the temperature of 15K, the reaction channel leading to CH5+ is preferred over the D-atom abstraction channel (isotope effect).Im Rahmen dieser Arbeit wurden zwei Apparaturen mit 22-Pol-Ionenfallen benutzt, um protonierte Wassercluster H+(H2O)n (n=4..10) und kleine ionische Kohlenwasserstoffe CHn+ (n=2..5) bei tiefen Temperaturen zu untersuchen. Die in einer Koronaentladungsquelle erzeugten Cluster H+(H2O)n wurden kinetisch und spektroskopisch untersucht. Dazu wurden sie in einem 22-Pol-Speicher mithilfe eines He-Puffergases auf einer Temperatur zwischen 80K und 350K thermalisiert. Die Bestimmung der Bindungsenergien fuer Cluster der Groesse n=4..10 wird ermoeglicht durch die Messung der temperaturabhaengigen Dissoziationsraten und durch die Ermittlung der inneren Energien mittels berechneter Schwingungsfrequenzen. Temperaturabhaengige IR-Spektren im Bereich der freien OH-Streckschwingung wurden aufgenommen. Die Austausch- und Abstreifreaktionen von ionischen Kohlenwasserstoffen CHn+ (n=2..5) mit H2, HD und D2 und die darauffolgenden Assoziationsprozesse wurden im Temperaturbereich 15K bis 300K untersucht. Es stellt sich z.B. heraus, dass der H-D-Austauschprozess zwischen CH5+ und HD bei 15K sehr langsam ist, wogegen CH3+ mit jeder Kollision einen Austausch ausfuehrt. In der Abstreifreaktion von CH4+ mit Wasserstoffmolekuelen beobachtet man eine inverse Temperaturabhaengigkeit. Dies wird vorlaeufig mit einer laengeren Komplexlebensdauer bei tiefen Temperaturen erklaert

VIBRATIONAL SPECTROSCOPY OF He-O2H+ AND O2H+

The elusive protonated oxygen, O$_2$H$^+$, has been characterized _x000d_ by vibrational action spectroscopy in a cryogenic 22-pole ion trap. On the one hand, the vibrational bands of the tagged He--O$_2$H$^+$ have been investigated, using a table-top OPO system for the known OH-stretch$^a$, whereas the FELIX$^b$ light source has been used to detect the hitherto unknown low-frequency O-O-H bend and O-O stretch._x000d_ On the other hand, the untagged O$_2$H$^+$ has been detected _x000d_ for the first time by high-resolution rovibrational spectroscopy_x000d_ via its $nu_1$ OH-stretch motion._x000d_ 38 ro-vibrational fine structure transitions with partly resolved hyperfine satellites were measured (56 resolved lines in total). _x000d_ Spectroscopic parameters were determined by a fit to an asymmetric rotor model with a $^3A''$ electronic ground state. _x000d_ The band center is at 3016.73~wn, which is in good _x000d_ agreement with experimental$^a$ and {it ab initio}$^{c,d}$ predictions. Based on the spectroscopic parameters, the rotational spectrum is predicted, but not detected yet. \_x000d_ _x000d_ noindent_x000d_ $^a$ S. A. Nizkorodov et al., Chem. Phys. Lett., 278, 26, 1997 \_x000d_ $^b$ D. Oepts et al., Infrared Phys. Technol., 36, 297, 1995 \_x000d_ $^c$ S. L. W. Weaver et al., Astrophys. J., 697, 601, 2009 \_x000d_ $^d$ X. Huang and T. J. Lee, J. Chem. Phys., 129, 044312, 2008 \_x000d_ _x000d

Rotational action spectroscopy of trapped molecular ions

Rotational action spectroscopy is an experimental method in which rotational spectra of molecules, typically in the microwave to sub-mm-wave domain of the electromagnetic spectrum (similar to 1-1000 GHz), are recorded by action spectroscopy. Action spectroscopy means that the spectrum is recorded not by detecting the absorption of light by the molecules, but by the action of the light on the molecules, e.g., photon-induced dissociation of a chemical bond, a photon-triggered reaction, or photodetachment of an electron. Typically, such experiments are performed on molecular ions, which can be well controlled and mass-selected by guiding and storage techniques. Though coming with many advantages, the application of action schemes to rotational spectroscopy was hampered for a long time by the small energy content of a corresponding photon. Therefore, the first rotational action spectroscopic methods emerged only about one decade ago. Today, there exists a toolbox full of different rotational action spectroscopic schemes which are summarized in this review

Searching for new symmetry species of CH5+ - From lines to states without a model

CH5+ is a prototype of an extremely flexible molecule for which the quantum states have eluded an analytical description so far. Therefore, the reconstruction of its quantum states relies on methods as e.g. the search for accumulations of combination differences of rovibrational transitions. Using the available high resolution data of the Cologne laboratories [1], this reconstruction has been improved by using the properties of kernel density estimators as well as new combinatorial approaches to evaluate the found accumulations. Two new symmetry sets have been discovered, and the known ones extended, with 1063 of the 2897 measured lines assigned, which is a significant improvement over the 65 assignments of the previous work. This allowed us not only to reconstruct more parts of the ground state levels, but also of the vibrationally excited states of CH5+. (C) 2017 Elsevier Inc. All rights reserved