The millimeter-wave spectrum and astronomical search of succinonitrile and its vibrational excited states ☠.

CONTEXT: Dinitriles with a saturated hydrocarbon skeleton and a -C≡N group at each end can have large electric dipole moments. Their formation can be related to highly reactive radicals such as CH2CN, C2N or CN. Thus, these saturated dinitriles are potential candidates to be observed in the ISM. AIMS: Our goal is the investigation of the rotational spectrum of one of the simplest dinitriles N≡C-CH2-CH2-C≡N, succinonitrile, whose actual rotational parameters are not precise enough to allow its detection in the ISM. In addition, the rotational spectra for its vibrational exicted states will be analyzed. METHODS: The rotational spectra of succinonitrile was measured in the frequency range 72-116.5 GHz using a new broadband millimeter-wave spectrometer based on radio astronomy receivers with Fast Fourier Transform backends. The identification of the vibrational excited states of succinonitrile was supported by high-level ab initio calculations on the harmonic and anharmonic force fields. RESULTS: A total of 459 rotational transitions with maximum values of J and Ka quantum numbers 70 and 14, respectively, were measured for the ground vibrational state of succinonitrile. The analysis allowed us to accurately determine the rotational, quartic and sextic centrifugal distortion constants. Up to eleven vibrational excited states, resulting from the four lowest frequency vibrational modes ν 13, ν 12, ν 24 and ν 23 were identified. In addition to the four fundamental modes, we observed overtones together with some combination states. The rotational parameters for the ground state were employed to unsuccessfully search for succinonitrile in the cold and warm molecular clouds Orion KL, Sgr B2(N), B1-b and TMC-1, using the spectral surveys captured by IRAM 30m at 3mm and the Yebes 40m at 1.3cm and 7mm.

Broad band high resolution rotational spectroscopy for Laboratory Astrophysics.

We present a new experimental setup devoted to the study of gas phase molecules and processes using broad band high spectral resolution rotational spectroscopy. A reactor chamber has been equipped with radio receivers similar to those used by radio astronomers to search for molecular emission in space. The whole Q (31.5-50 GHz) and W bands (72-116.5 GHz) are available for rotational spectroscopy observations. The receivers are equipped with 16×2.5 GHz Fast Fourier Transform spectrometers with a spectral resolution of 38.14 kHz allowing the simultaneous observation of the complete Q band and one third of the W band. The whole W band can be observed in three settings in which the Q band is always observed. Species such as CH3CN, OCS, and SO2 are detected, together with many of their isotopologues and vibrationally excited states, in very short observing times. The system permits automatic overnight observations and integration times as long as 2.4×105 seconds have been reached. The chamber is equipped with a radiofrequency source to produce cold plasmas and with four ultraviolet lamps to study photochemical processes. Plasmas of CH4, N2, CH3CN, NH3, O2, and H2, among other species, have been generated and the molecular products easily identified by their rotational spectrum, and mass spectrometry and optical spectroscopy. Finally, the rotational spectrum of the lowest energy conformer of CH3CH2NHCHO (N-Ethylformamide), a molecule previously characterized in microwave rotational spectroscopy, has been measured up to 116.5 GHz allowing the accurate determination of its rotational and distortion constants and its search in space.

Stability of CH3NCO in astronomical ices under energetic processing. A laboratory study.

Methyl isocyanate (CH3NCO) was recently found in hot cores and suggested on comet 67P/CG. The incorporation of this molecule into astrochemical networks requires data on its formation and destruction. In this work, ices of pure CH3NCO and of CH3NCO(4-5%)/H2O mixtures deposited at 20 K were irradiated with a UV D2 lamp (120-400 nm) and bombarded by 5 keV electrons to mimic the secondary electrons produced by cosmic rays (CRs). The destruction of CH3NCO was studied using IR spectroscopy. After processing, the νa-NCO band of CH3NCO disappeared and IR bands corresponding to CO, CO2, OCN- and HCN/CN- appeared instead. The products of photon and electron processing were very similar. Destruction cross sections and half-life doses were derived from the measurements. Water ice provides a good shield against UV irradiation (half-life dose of ~ 64 eV molecule-1 for CH3NCO in water-ice), but not so good against high-energy electrons (half-life dose ~ 18 eV molecule-1). It was also found that CH3NCO does not react with H2O over the 20-200 K temperature range. These results indicate that hypothetical CH3NCO in the ices of dense clouds should be stable against UV photons and relatively stable against CRs over the lifetime of a cloud (~ 107 yr), and could sublime in the hot core phase. On the surface of a Kuiper belt object (the original location of comet 67P/CG) the molecule would be swiftly destroyed, both by photons and CRs, but embedded below just 10 µm of water-ice, the molecule could survive for ~ 109 yr.

Plasma generation and processing of interstellar carbonaceous dust analogs.

Interstellar (IS) dust analogs, based on amorphous hydrogenated carbon (a-C:H) were generated by plasma deposition in RF discharges of CH4 + He mixtures. The a-C:H samples were characterized by means of secondary electron microscopy (SEM), infrared (IR) spectroscopy and UV-visible reflectivity. DFT calculations of structure and IR spectra were also carried out. From the experimental data, atomic compositions were estimated. Both IR and reflectivity measurements led to similar high proportions (≈ 50%) of H atoms, but there was a significant discrepancy in the sp2/sp3 hybridization ratios of C atoms (sp2/sp3 = 1.5 from IR and 0.25 from reflectivity). Energetic processing of the samples with 5 keV electrons led to a decay of IR aliphatic bands and to a growth of aromatic bands, which is consistent with a dehydrogenation and graphitization of the samples. The decay of the CH aliphatic stretching band at 3.4 µm upon electron irradiation is relatively slow. Estimates based on the absorbed energy and on models of cosmic ray (CR) flux indicate that CR bombardment is not enough to justify the observed disappearance of this band in dense IS clouds.

Precisely controlled fabrication, manipulation and in-situ analysis of Cu based nanoparticles.

The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu0 to CuO through Cu2O, and their mixtures) at different stages in the machine.

Using radio astronomical receivers for molecular spectroscopic characterization in astrochemical laboratory simulations: A proof of concept.

We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactors and the performances of the resulting setup for spectroscopy and chemical simulations in laboratory astrophysics. Several experiments including cold plasma generation and UV photochemistry were performed in a 40 cm long gas cell placed in the beam path of the Aries 40 m radio telescope receivers operating in the 41-49 GHz frequency range interfaced with fast Fourier transform spectrometers providing 2 GHz bandwidth and 38 kHz resolution. The impedance matching of the cell windows has been studied using different materials. The choice of the material and its thickness was critical to obtain a sensitivity identical to that of standard radio astronomical observations. Spectroscopic signals arising from very low partial pressures of CH3OH, CH3CH2OH, HCOOH, OCS, CS, SO2 (<10-3 mbar) were detected in a few seconds. Fast data acquisition was achieved allowing for kinetic measurements in fragmentation experiments using electron impact or UV irradiation. Time evolution of chemical reactions involving OCS, O2 and CS2 was also observed demonstrating that reactive species, such as CS, can be maintained with high abundance in the gas phase during these experiments.

Laboratory study of methyl isocyanate ices under astrophysical conditions.

Methyl isocyanate has been recently detected in comet 67P/ Churyumov-Gerasimenko (67P/CG) and in the interstellar medium. New physicochemical studies on this species are now necessary as tools for subsequent studies in astrophysics. In this work, infrared spectra of solid CH3NCO have been obtained at temperatures of relevance for astronomical environments. The spectra are dominated by a strong, characteristic multiplet feature at 2350-2250 cm-1, which can be attributed to the antisymmetric stretching of the NCO group. A phase transition from amorphous to crystalline methyl isocyanate is observed at ~ 90 K. The band strengths for the absorptions of CH3NCO in ice at 20 K have been measured. Deuterated methyl isocyanate is used to help with the spectral assignment. No X-ray structure has been reported for crystalline CH3NCO. Here we advance a tentative theoretical structure, based on Density Functional Theory (DFT) calculations, derived taking as a starting point the crystal of isocyanic acid. A harmonic theoretical spectrum is calculated then for the proposed structure, and compared with the experimental data. A mixed ice of H2O and CH3NCO was formed by simultaneous deposition of water and methyl isocyanate at 20 K. The absence of new spectral features indicates that methyl isocyanate and water do not react appreciably at 20 K, but form a stable mixture. The high CH3NCO/H2O ratio reported for comet 67P/CG, and the characteristic structure of the 2350-2250 cm-1 band, make of it a very good candidate for future astronomical searches.

The High Resolution Infrared Spectrum of HCl.

The chloroniumyl cation, HCl+, has been recently identified in space from Herschel's spectra. A joint analysis of extensive vis-UV spectroscopy emission data together with a few high-resolution and high-accuracy millimiter-wave data provided the necessary rest frequencies to support the astronomical identification. Nevertheless, the analysis did not include any infrared (IR) vibration-rotation data. Furthermore, with the end of the Herschel mission, infrared observations from the ground may be one of the few available means to further study this ion in space. In this work, we provide a set of accurate rovibrational transition wavenumbers as well as a new and improved global fit of vis-UV, IR and millimiter-wave spectroscopy laboratory data, that will aid in future studies of this molecule.

Chemistry in glow discharges of H2 / O2 mixtures. Diagnostics and modelling.

The chemistry of low pressure H2 + O2 discharges with different mixture ratios has been studied in a hollow cathode DC reactor. Neutral and positive ion distributions have been measured by mass spectrometry, and Langmuir probes have been used to provide charge densities and electron temperatures. A simple zero order kinetic model including neutral species and positive and negative ions, which takes into account gas-phase and heterogeneous chemistry, has been used to reproduce the global composition of the plasmas over the whole range of mixtures experimentally studied, and allows for the identification of the main physicochemical mechanisms that may explain the experimental results. To our knowledge, no combined experimental and modelling studies of the heavy species kinetics of low pressure H2 + O2 plasmas including ions has been reported before. As expected, apart from the precursors, H2O is detected in considerable amounts. The model also predicts appreciable concentrations of H and O atoms and the OH radical. The relevance of the metastable species O(1D) and O2(a1Δg) is analysed. Concerning the charged species, positive ion distributions are dominated by H3O+ for a wide range of intermediate mixtures, while H3+ and O2+ are the major ions for the higher and lower H2/O2 ratios, respectively. The mixed ions OH+, H2O+ and HO2+ are also observed in small amounts. Negative ions are shown to have a limited relevance in the global chemistry; their main contribution is the reduction of the electron density available for electron impact processes.

Ion chemistry in cold plasmas of H2 with CH4 and N2.

The distributions of ions and neutrals in low-pressure (approximately 10(-2) mbar) DC discharges of pure hydrogen and hydrogen with small admixtures (5%) of CH(4) and N(2) have been determined by mass spectrometry. Besides the mentioned plasma precursors, appreciable amounts of NH(3) and C(2)H(x) hydrocarbons, probably mostly from wall reactions, are detected in the gas phase. Primary ions, formed by electron impact in the glow region, undergo a series of charge transfer and reactive collisions that determine the ultimate ion distribution in the various plasmas. A comparison of the ion mass spectra for the different mixtures, taking into account the mass spectra of neutrals, provides interesting information on the key reactions among ions. The prevalent ion is H3+ in all cases, and the ion chemistry is dominated by protonation reactions of this ion and some of its derivatives. Besides the purely hydrogenic ions, N(2)H+, NH(4)+, and CH(5)+ are found in significant amounts. The only mixed C/N ion clearly identified is protonated acetonitrile C(2)H(4)N+. The results suggest that very little HCN is formed in the plasmas under study.

Atom and ion chemistry in low pressure hydrogen dc plasmas.

The chemical composition of a low-pressure hydrogen dc plasma produced in a hollow cathode discharge has been measured and modeled. The concentrations of H atoms and of H(+), H(2)(+) and H(3)(+) ions were determined with a combination of optical spectroscopic and mass spectrometric techniques, over the range of pressures (p approximately 0.008-0.2 m bar) investigated. The results were rationalized with the help of a zero-order kinetic model. A comparatively high fraction ( approximately 0.1+/-0.05) of H atoms, indicative of a relatively small wall recombination, was observed. Low ionization degrees (<10(-4)) were obtained in all cases. In general, the ionic composition of the plasma was found to be dominated by H(3)(+), except at the lowest pressures, where H(2)(+) was the major ion. The key physicochemical processes determining the plasma composition were identified from the comparison of experimental and model results, and are discussed in the paper.

Influence of rotation and isotope effects on the dynamics of the N((2)D)+H(2) reactive system and of its deuterated variants.

Integral cross sections and thermal rate constants have been calculated for the N((2)D)+H(2) reaction and its isotopic variants N((2)D)+D(2) and the two-channel N((2)D)+HD by means of quasiclassical trajectory and statistical quantum-mechanical model methods on the latest ab initio potential-energy surface [T.-S. Ho et al., J. Chem. Phys. 119, 3063 (2003)]. The effect of rotational excitation of the diatom on the dynamics of these reactions has been investigated and interesting discrepancies between the classical and statistical model calculations have been found. Whereas a net effect of reagent rotation on reactivity is always observed in the classical calculations, only a very slight effect is observed in the case of the asymmetric N((2)D)+HD reaction for the statistical quantum-mechanical method. The thermal rate constants calculated on this Potential-Energy Surface using quasiclassical trajectory and statistical model methods are in good agreement with the experimental determinations, although the latter are somewhat larger. A reevaluation of the collinear barrier of the potential surface used in the present study seems timely. Further theoretical and experimental studies are needed for a full understanding of the dynamics of the title reaction.

Low-pressure DC air plasmas. investigation of neutral and ion chemistry.

The neutral and charged species present in a direct current (dc) hollow cathode, gas flow, air reactor are experimentally studied by quadrupole mass spectrometry. The degree of ionization of the plasma and the electron mean temperature with decreasing air pressure, for constant discharge current, are measured with a double Langmuir probe. The chemical composition of the plasma changes appreciably over the 3 x 10(-3) to 5 x 10(-2) mbar range investigated: at the lowest pressures studied, O2 dissociation is up to 60% and the concentration of NO is half that of N2; concerning ions, NO+ and N2+ are dominant for the whole pressure range. A kinetic model of the plasma including electrons, neutrals, and positive ions is developed to account for the experimental observations; it is consistent with energy balance and predicts that heterogeneous processes are the main source of NO and that the contribution of ions to the global chemistry of neutrals is of minor significance even for the lowest pressures.

Low-temperature rotational relaxation of CO in self-collisions and in collisions with Ne and He.

The low-temperature rotational relaxation of CO in self-collisions and in collisions with the rare-gas atoms Ne and He has been investigated in supersonic expansions with a combination of resonance-enhanced multiphoton ionization (REMPI) spectroscopy and time-of-flight techniques. For the REMPI detection of CO, a novel 2 + 1' scheme has been employed through the A(1)Pi state of CO. From the measured data, average cross sections for rotational relaxation have been derived as a function of temperature in the range 5-100 K. For CO-Ne and CO-He, the relaxation cross sections grow, respectively, from values of approximately 20 and 7 A(2) at 100 K to values of approximately 65-70 and approximately 20 A(2) in the 5-20 K temperature range. The cross section for the relaxation of CO-CO grows from a value close to 40 A(2) at 100 K to a maximum of 60 A(2) at 20 K and then decreases again to 40 A(2) at 5 K. These results are qualitatively similar to those obtained previously with the same technique for N(2)-N(2), N(2)-Ne, and N(2)-He collisions, although in the low-temperature range (T < 20 K) the CO relaxation cross sections are significantly larger than those for N(2). Some discrepancies have been found between the present relaxation cross sections for CO-CO and CO-He and the values derived from electron-induced fluorescence experiments.