Millimeter-wave Spectrometer Research Articles

The Non-Thermal Radio Emissions of the Solar Transition Region and the Proposal of an Observational Regime

The transition region is a very thin but most peculiar layer in the solar atmosphere located between the solar chromosphere and the corona. It is a key region for understanding coronal heating, solar eruption triggers, and the origin of solar winds. Here, almost all physical parameters (density, temperature, and magnetic fields) have the maximum gradient. Therefore, this region should be highly dynamic, including fast energy releasing and transporting, plasma heating, and particle accelerating. The physical processes can be categorized into two classes: thermal and non-thermal processes. Thermal processes can be observed at ultraviolet (UV) and extreme ultraviolet (EUV) wavelengths via multi-wavelength images. Non-thermal processes accelerate non-thermal electrons and produce radio emissions via the gyrosynchrotron mechanism resulting from the interaction between the non-thermal electrons and magnetic fields. The frequency range spans from several GHz to beyond 100 GHz, in great number of bursts with narrowband, millisecond lifetime, rapid frequency drifting rates, and being referred to as transition region small-scale microwave bursts (TR-SMBs). This work proposes a new type of Solar Ultra-wide Broadband Millimeter-wave Spectrometer (SUBMS) that can be used to observe TR-SMBs. From SUBMS observations, we can derive rich dynamic information about the transition region, such as information about non-thermal energy release and propagation, the flows of plasma and energetic particles, the magnetic fields and their variations, the generation and transportation of various waves, and the formation and evolution of the source regions of solar eruptions. Such an instrument can actually detect the non-thermal signals in the transition region during no flare as well as the eruptive high-energy processes during solar flares.

The C2H4O isomers in the oxidation of ethylene

A combined rotational spectroscopy, thermochemistry, and kinetic modeling study explores the mechanism of acetaldehyde (ethanal), vinyl alcohol (ethenol), and ethylene oxide (oxirane) formation in the oxidation of ethylene (ethene). Multiplexed quantitative detection of oxidation intermediates and products exiting a SiO2/SiC microreactor at 1700 K is demonstrated with the BrightSpec W-band chirped-pulse Fourier transform millimeter-wave spectrometer. The broadband rotational spectrum contains transitions of formaldehyde (CH2O), methoxy (CH3O), methanol (CH3OH), ketene (CH2CO), acetaldehyde (CH3CHO), syn-vinyl alcohol (syn-CH2CHOH), anti-vinyl alcohol (anti-CH2CHOH), oxirane (c-CH2OCH2), propyne (CH3CCH), and syn-propanal (syn-CH3CH2CHO). We focus on the three C2H4O species and deduce their concentration ratio [CH3CHO]:[CH2CHOH]:[c-CH2OCH2] = 1:0.7(2):0.06(2) by comparing the observed line intensities to those simulated with the PGOPHER software. Detailed thermochemistry of the C2H4O isomers and conformers is provided by Active Thermochemical Tables. The observed excess concentrations of vinyl alcohol and oxirane relative to the more stable acetaldehyde compared to the equilibrium ratio at 1700 K (1:0.087:0.000024), point to direct chemical pathways to these higher energy isomers. The mechanism for the formation of the three C2H4O isomers is analyzed using a 0-D homogenous reactor kinetics simulation for ethylene oxidation. The ratios of the C2H4O isomers concentrations predicted by the kinetic model are compared to the experimental values.

Microwave radiometer observations of the ozone diurnal cycle and its short-term variability over Switzerland

Abstract. In Switzerland, two ground-based ozone microwave radiometers are operated in the vicinity of each other (ca. 40 km): the GROund-based Millimeter-wave Ozone Spectrometer (GROMOS) in Bern (Institute of Applied Physics) and the Stratospheric Ozone MOnitoring RAdiometer (SOMORA) in Payerne (MeteoSwiss). Recently, their calibration and retrieval algorithms have been fully harmonized, and updated time series are now available since 2009. Using these harmonized ozone time series, we investigate and cross-validate the strato–mesospheric ozone diurnal cycle derived from the two instruments and compare it with various model-based datasets: the dedicated GEOS-GMI Diurnal Ozone Climatology (GDOC) based on the Goddard Earth Observing System (GEOS-5) general circulation model, the Belgian Assimilation System for Chemical ObsErvations (BASCOE) – a chemical transport model driven by ERA5 dynamics, and a set of free-running simulations from the Whole Atmosphere Community Climate Model (WACCM). Overall, the two instruments show very similar ozone diurnal cycles at all seasons and pressure levels, and the models compare well with each other. There is a good agreement between the models and the measurements at most seasons and pressure levels, and the largest discrepancies can be explained by the limited vertical resolution of the microwave radiometers. However, as in a similar study over Mauna Loa, some discrepancies remain near the stratopause, at the transition region between ozone daytime accumulation and depletion. We report similar delays in the onset of the modelled ozone diurnal depletion in the lower mesosphere. Using the newly harmonized time series of GROMOS and SOMORA radiometers, we present the first observations of short-term (sub-monthly) ozone diurnal cycle variability at mid-latitudes. The short-term variability is observed in the upper stratosphere during wintertime, when the mean monthly cycle has a small amplitude and when the dynamics are more important. This is shown in the form of strong enhancements of the diurnal cycle, reaching up to 4–5 times the amplitude of the mean monthly cycle. We show that BASCOE is able to capture some of these events, and we present a case study of one such event following the minor sudden stratospheric warming of January 2015. Our analysis of this event supports the conclusions of a previous modelling study, attributing regional variability of the ozone diurnal cycle to regional anomalies in nitrogen oxide (NOx) concentrations. However, we also find periods with an enhanced diurnal cycle that do not show much change in NOx and where other processes might be dominant (e.g. atmospheric tides). Given its importance, we believe that the short-term variability of the ozone diurnal cycle should be further investigated over the globe, for instance using the BASCOE model.

Dual-band Fourier-transform Millimeter-wave Spectrometry for In Situ Gas Sensing

The exploration of icy body composition in the solar system has often involved spectroscopic measurements of volatiles detected with remote sensing, such measurements portray materials naturally expelled from the surface that enter the exosphere and potentially escape into space. Variations in the ratio of deuterium and hydrogen in these measurements have led to inconclusive hypotheses regarding potential cometary origins of Earth’s ocean water and/or organics. Observational biases regarding unknown previous processing of the observable ejected materials necessitates studies of more dormant, less-processed bodies. Landed missions on comets have brought focus onto the development of small, sensitive instrumentation capable of similar composition measurements of the nascent surface and near-surface materials. We present an evolution of our compact Fourier-transform millimeter-wave cavity spectrometer that is tuned for sensitivity at 80.6 and 183 GHz where HDO and H2O exhibit resonance features. We discuss both a low-SWaP (size–weight and power) architecture that uses custom microchip transceiver elements as well as a modular configuration using traditional GaAs-based millimeter-wave hardware. New design features for these systems including quartz-based coupling elements, system thermal management, and a separable clocking board are discussed in addition to sensitivity studies and applications in potential mission scenarios.

Searches for bridged bicyclic molecules in space-norbornadiene and its cyano derivatives.

The norbornadiene (NBD) molecule, C7H8, owes its fame to its remarkable photoswitching properties that are promising for molecular solar-thermal energy storage systems. Besides this photochemical interest, NBD is a rather unreactive species within astrophysical conditions and it should exhibit high photostability, properties that might also position this molecule as an important constituent of the interstellar medium (ISM)-especially in environments that are well shielded from short-wavelength radiation, such as dense molecular clouds. It is thus conceivable that, once formed, NBD can survive in dense molecular clouds and act as a carbon sink. Following the recent interstellar detections of large hydrocarbons, including several cyano-containing ones, in the dense molecular cloud TMC-1, it is thus logical to consider searching for NBD-which presents a shallow but non-zero permanent electric dipole moment (0.06 D)-as well as for its mono- and dicyano-substituted compounds, referred to as CN-NBD and DCN-NBD, respectively. The pure rotational spectra of NBD, CN-NBD, and DCN-NBD have been measured at 300 K in the 75-110 GHz range using a chirped-pulse Fourier-transform millimetre-wave spectrometer. Of the three species, only NBD was previously studied at high resolution in the microwave domain. From the present measurements, the derived spectroscopic constants enable prediction of the spectra of all three species at various rotational temperatures (up to 300 K) in the spectral range mapped at high resolution by current radio observatories. Unsuccessful searches for these molecules were conducted toward TMC-1 using the QUIJOTE survey, carried out at the Yebes telescope, allowing derivation of the upper limits to the column densities of 1.6 × 1014 cm-2, 4.9 × 1010 cm-2, and 2.9 × 1010 cm-2 for NBD, CN-NBD, and DCN-NBD, respectively. Using CN-NBD and cyano-indene as proxies for the corresponding bare hydrocarbons, this indicates that-if present in TMC-1-NBD would be at least four times less abundant than indene.

Laboratory spectroscopy of allylimine and tentative detection towards the G+0.693-0.027 molecular cloud

Context. Substituted methanimines and ethylenes have been identified in the interstellar medium. Therefore, allylimine (CH2 =CH–CH=NH) represents a promising candidate for a new interstellar detection. Aims. The goal of the present work is to perform a comprehensive laboratory investigation of the rotational spectrum of allylimine in its ground vibrational state in order to obtain a highly precise set of rest frequencies to assist its search for astronomical sources. Methods. The rotational spectra of the two most stable trans–anti and trans–syn geometrical isomers of allylimine were recorded in the laboratory in the 84–300 GHz frequency interval. Measurements were performed using a source-modulation millimetre-wave spectrometer equipped with a pyrolysis system for the production of unstable species. High-level ab initio calculations were performed to assist the analysis and to obtain reliable estimates for an extended set of spectroscopic parameters. Guided by new laboratory data, allylimine was searched for in space using a sensitive spectral survey of the G+0.693-0.027 molecular cloud, located at the Galactic centre. Results. Almost 1000 rotational transitions have been recorded for trans–anti and trans–syn allylimine. These new data have enabled the determination of a very accurate set of spectroscopic parameters including rotational, quartic and sextic centrifugal distortion con-stants, as well as nuclear quadrupole coupling constants. The improved spectral data allowed us to report a tentative detection for both allylimine isomers in the G+0.693-0.027 molecular cloud, located at the Galactic centre.

Toward the limits of complexity of interstellar chemistry: Rotational spectroscopy and astronomical search for n- and i-butanal

Context. In recent times, large organic molecules of exceptional complexity have been found in diverse regions of the interstellar medium. Aims. In this context, we aim to provide accurate frequencies of the ground vibrational state of two key aliphatic aldehydes, n-butanal and its branched-chain isomer, i-butanal, to enable their eventual detection in the interstellar medium. We also want to test the level of complexity that interstellar chemistry can reach in regions of star formation. Methods. We employ a frequency modulation millimeter-wave absorption spectrometer to measure the rotational features of n- and i-butanal. We analyze the assigned rotational transitions of each rotamer separately using the A-reduced semirigid-rotor Hamiltonian. We use the spectral line survey ReMoCA performed with the Atacama Large Millimeter/submillimeter Array to search for n- and i-butanal toward the star-forming region Sgr B2(N). We also search for both aldehydes toward the molecular cloud G+0.693−0.027 with IRAM 30 m and Yebes 40 m observations. The observational results are compared with computational results from a recent gas-grain astrochemical model. Results. Several thousand rotational transitions belonging to the lowest-energy conformers of two distinct linear and branched isomers have been assigned in the laboratory spectra up to 325 GHz. A precise set of the relevant rotational spectroscopic constants has been determined for each structure as a first step toward identifying both molecules in the interstellar medium. We report non-detections of n-and i-butanal toward both sources, Sgr B2(N1S) and G+0.693-0.027. We find that n- and i-butanal are at least 2-6 and 6-18 times less abundant than acetaldehyde toward Sgr B2(N1S), respectively, and that n-butanal is at least 63 times less abundant than acetaldehyde toward G+0.693−0.027. While propanal is not detected toward Sgr B2(N1S) either, with an abundance at least 5–11 lower than that of acetaldehyde, propanal is found to be 7 times less abundant than acetaldehyde in G+0.693−0.027. Comparison with astrochemical models indicates good agreement between observed and simulated abundances (where available). Grain-surface chemistry appears sufficient to reproduce aldehyde ratios in G+0.693−0.027; gas-phase production may play a more active role in Sgr B2(N1S). Model estimates for the larger aldehydes indicate that the observed upper limits may be close to the underlying values. Conclusions. Our astronomical results indicate that the family of interstellar aldehydes in the Galactic center region is characterized by a drop of one order of magnitude in abundance at each incrementation in the level of molecular complexity.

Micro- and millimeter-wave spectra of five conformers of cysteamine and their interstellar search

Context. Cysteamine (NH2CH2CH2SH), a molecule of potential astrobiological interest, has not yet been detected in the interstellar medium. Furthermore, the sulfur- stituted isomer of ethanolamine (or 2-aminoethanol) has been recently detected in the molecular cloud G+0.693–0.027. Aims. In order to conduct a new interstellar search for cysteamine in the molecular cloud G+0.693–0.027, its pure rotational spectrum needs to be investigated in the laboratory. Methods. A pulsed-jet Fourier transform microwave spectrometer and a Stark-modulated free-jet millimeter-wave absorption spectrometer were used to measure the purely rotational spectrum of cysteamine in the range of 6.5-18 GHz (46.12–16.66 mm) and 59.6–120.0 GHz (5.03–2.72 mm), respectively. We used a deep spectral line survey toward the molecular cloud G+0.693-0.027 obtained with the IRAM 30 m and Yebes 40 m radiotelescopes to search for cysteamine. Results. We assigned 815 rotational transition lines of five conformers (gGt, gGg, g′Gg, g′Gg′, and g'Gt) to fit the rotational constants, quartic centrifugal distortion constants, and the 14N nuclear quadrupole coupling constants. For four conformers (gGt, gGg, g′Gg, and g′Gg′), the 34S isotopologs were observed, and for two of them (gGg and g'Gg), the 13C and 15N isotopolog spectra were also detected; all in natural abundance. The five conformers of cysteamine were not detected toward the G+0.693–0.027 molecular cloud. We derived upper limits for their molecular abundances compared to molecular hydrogen of <(0.2–1.3) × 10–10. The relative abundances with respect to the oxygen counterpart ethanolamine, previously detected toward this cloud, are NH2CH2CH2OH/NH2CH2CH2SH > 0.8–5.3.

Skeletal Torsion Tunneling and Methyl Internal Rotation: The Coupled Large Amplitude Motions in Phenyl Acetate.

The rotational spectrum of phenyl acetate, CH3COOC6H5, is measured using a free jet absorption millimeter-wave spectrometer in the range from 60 to 78 GHz and two pulsed jet Fourier transform microwave spectrometers covering a total frequency range from 2 to 26.5 GHz. The features of two large amplitude motions, the methyl group internal rotation and the skeletal torsion of the CH3COO group with respect to the phenyl ring C6H5 (tilted at about 70°), characterize the spectrum. The vibrational ground state is split into four widely spaced sublevels, labeled as A0, E0, A1, and E1, each of them with its set of rotational transitions and with additional interstate transitions. A global fit of the line frequencies of the four sublevels leads to the determination of 51 spectroscopic parameters, including the ΔEA0/A1 and ΔEE0/E1 vibrational splittings of ~36.4 and ~33.5 GHz, respectively. The V3 barrier to methyl internal rotation (~136 cm−1) and the skeletal torsion B2 barrier to the orthogonality of the two planes (~68 cm−1) are deduced.

Investigation and amelioration of long-term instrumental drifts in water vapor and nitrous oxide measurements from the Aura Microwave Limb Sounder (MLS) and their implications for studies of variability and trends

Abstract. The Microwave Limb Sounder (MLS), launched on NASA's Aura spacecraft in 2004, measures vertical profiles of the abundances of key atmospheric species from the upper troposphere to the mesosphere with daily near-global coverage. We review the first 15 years of the record of H2O and N2O measurements from the MLS 190 GHz subsystem (along with other 190 GHz information), with a focus on their long-term stability, largely based on comparisons with measurements from other sensors. These comparisons generally show signs of an increasing drift in the MLS “version 4” (v4) H2O record starting around 2010. Specifically, comparisons with v4.1 measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) indicate a ∼ 2 %–3 % per decade drift over much of the stratosphere, increasing to as much as ∼ 7 % per decade around 46 hPa. Larger drifts, of around 7 %–11 % per decade, are seen in comparisons to balloon-borne frost point hygrometer measurements in the lower stratosphere. Microphysical calculations considering the formation of polar stratospheric clouds in the Antarctic winter stratosphere corroborate a drift in MLS v4 water vapor measurements in that region and season. In contrast, comparisons with the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on NASA's Thermosphere Ionosphere Mesosphere Energetics and Dynamics (TIMED) mission, and with ground-based Water Vapor Millimeter-wave Spectrometer (WVMS) instruments, do not show statistically significant drifts. However, the uncertainty in these comparisons is large enough to encompass most of the drifts identified in other comparisons. In parallel, the MLS v4 N2O product is shown to be generally decreasing over the same period (when an increase in stratospheric N2O is expected, reflecting a secular growth in emissions), with a more pronounced drift in the lower stratosphere than that found for H2O. Comparisons to ACE-FTS and to MLS N2O observations in a different spectral region, with the latter available from 2004 to 2013, indicate an altitude-dependent drift, growing from 5 % per decade or less in the mid-stratosphere to as much as 15 % per decade in the lower stratosphere. Detailed investigations of the behavior of the MLS 190 GHz subsystem reveal a drift in its “sideband fraction” (the relative sensitivity of the 190 GHz receiver to the two different parts of the microwave spectrum that it observes). Our studies indicate that sideband fraction drift accounts for much of the observed changes in the MLS H2O product and some portion of the changes seen in N2O. The 190 GHz sideband fraction drift has been corrected in the new “version 5” (v5) MLS algorithms, which have now been used to reprocess the entire MLS record. As a result of this correction, the MLS v5 H2O record shows no statistically significant drifts compared to ACE-FTS. However, statistically significant drifts remain between MLS v5 and frost point measurements, although they are reduced. Drifts in v5 N2O are about half the size of those in v4 but remain statistically significant. Scientists are advised to use MLS v5 data in all future studies. Quantification of interregional and seasonal to annual changes in MLS H2O and N2O will not be affected by the drift. However, caution is advised in studies using the MLS record to examine long-term (multiyear) variability and trends in either of these species, especially N2O; such studies should only be undertaken in consultation with the MLS team. Importantly, this drift does not affect any of the MLS observations made in other spectral regions such as O3, HCl, CO, ClO, or temperature.

Structure and dynamics of methacrylamide, a computational and free-jet rotational spectroscopic study

The conformational space of methacrylamide was explored by quantum mechanical modeling and surveyed in the 59.6–104.0 GHz frequency range using a millimeter-wave Stark-modulated free-jet absorption spectrometer. According to the relative orientation of the two unsaturated bonds, two conformers were observed, namely s-trans (A=5234.360(1), B=3364.9717(8) and C=2173.099(1) MHz) and s-cis (A=5207.292(1), B=3470.930(1) and C=2113.496(1) MHz). The s-trans conformation is the global minimum, with relative energy 4(2) kJ mol−1 and calculated isomerization barrier 15 kJ mol−1. Except for the methyl hydrogen atoms, s-cis-methacrylamide is planar and its methyl internal rotation barrier is 10.2(1) kJ mol−1. In s-trans-methacrylamide the allyl and amino frames form a dihedral angle of about 30° and the methyl internal rotation barrier is 7.4 kJ mol−1. This different behaviour is explained in terms of attractive and repulsive intramolecular interactions between groups: CH2/CO and CH3/NH2 for s-cis, CH2/NH2 and CH3/CO for s-trans. The tunneling splitting related to the double-well potential describing the interconversion between the two equivalent s-trans forms is 837.97(2) MHz and was reproduced by a one-dimensional flexible model using a 3.6 kJ mol−1 interconversion barrier.

Clinical assessment of W-band spectroscopy for non-invasive detection and monitoring of sustained hyperglycemia.

HbA1c is the gold standard test for monitoring medium/long term glycemia conditions in diabetes care, which is a critical factor in reducing the risk of chronic diabetes complications. Current technologies for measuring HbA1c concentration are invasive and adequate assays are still limited to laboratory-based methods that are not widely available worldwide. The development of a non-invasive diagnostic tool for HbA1c concentration can lead to the decrease of the rate of undiagnosed cases and facilitate early detection in diabetes care. We present a preliminary validation diagnostic study of W-band spectroscopy for detection and monitoring of sustained hyperglycemia, using the HbA1c concentration as reference. A group of 20 patients with type 1 diabetes mellitus and 10 healthy subjects were non-invasively assessed at three different visits over a period of 7 months by a millimeter-wave spectrometer (transmission mode) operating across the full W-band. The relationship between the W-band spectral profile and the HbA1c concentration is studied using longitudinal and non-longitudinal functional data analysis methods. A potential blind discrimination between patients with or without diabetes is obtained, and more importantly, an excellent relation (R-squared = 0.97) between the non-invasive assessment and the HbA1c measure is achieved. Such results support that W-band spectroscopy has great potential for developing a non-invasive diagnostic tool for in-vivo HbA1c concentration monitoring in humans.

Intramolecular H-Bond Dynamics of Catechol Investigated by THz High-Resolution Spectroscopy of Its Low-Frequency Modes.

Catechol is an oxygenated aromatic volatile organic compound and a biogenic precursor of secondary organic aerosols. Monitoring this compound in the gas phase is desirable due to its appreciable reactivity with tropospheric ozone. From a molecular point of view, this molecule is attractive since the two adjacent hydroxy groups can interchangeably act as donor and acceptor in an intramolecular hydrogen bonding due to the tunnelling between two symmetrically equivalent structures. Using synchrotron radiation, we recorded a rotationally-resolved Fourier Transform far-infrared (IR) spectrum of the torsional modes of the free and bonded -OH groups forming the intramolecular hydrogen bond. Additionally, the room temperature, pure rotational spectrum was measured in the 70–220 frequency range using a millimeter-wave spectrometer. The assignment of these molecular transitions was assisted by anharmonic high-level quantum-chemical calculations. In particular, pure rotational lines belonging to the ground and the four lowest energy, vibrationally excited states were assigned. Splitting due to the tunnelling was resolved for the free -OH torsional state. A global fit combining the far-IR and millimeter-wave data provided the spectroscopic parameters of the low-energy far-IR modes, in particular those characterizing the intramolecular hydrogen bond dynamics.

Rotational spectroscopy and bound state calculations of deuterated NH3–H2 van der Waals complexes

Pure rotational transitions of the deuterated NH3–H2 weakly bound complexes formed by NH3/ND3 and H2/D2, namely ND3–H2, NH3–D2 and ND3–D2, have been detected. Three different techniques, a millimeter-wave intracavity jet OROTRON spectrometer, molecular beam Fourier transform microwave (FTMW) cavity spectrometer and the broadband chirped pulse (CP) FTMW spectrometer were used to record the spectra in the frequency range from 20 to 140 GHz. The double resonance method was additionally applied to extend the frequency range of the OROTRON spectrometer to lower and of the FTMW cavity spectrometer to higher frequencies. A search for the transitions of deuterated isotopologues and their assignments were based on the recent study of the main isotopic species NH3–H2 [L.A. Surin et al., Astrophys. J., 838, 27 (2017)] and further confirmed by the bound state calculations presented here. The measured line positions including hyperfine splitting due to the 14N nuclear spin of NH3/ND3 and the D nuclear spins of D2 were analysed in order to determine the molecular parameters and structure of the deuterated NH3–H2 complexes. This study provides an effective new probe of the intermolecular interaction between ammonia and dihydrogen, knowledge of which is important for numerical modelling of astrophysical environments.

Propargylimine in the laboratory and in space: millimetre-wave spectroscopy and its first detection in the ISM

Context. Small imines containing up to three carbon atoms are present in the interstellar medium (ISM). As alkynyl compounds are abundant in this medium, propargylimine (2-propyn-1-imine, HC ≡C−CH =NH) thus represents a promising candidate for a new interstellar detection. Aims. The goal of the present work is to perform a comprehensive laboratory investigation of the rotational spectrum of propargylimine in its ground vibrational state in order to obtain a highly precise set of rest frequencies and to search for it in space. Methods. The rotational spectra of E and Z geometrical isomers of propargylimine have been recorded in the laboratory in the 83–500 GHz frequency interval. The measurements have been performed using a source-modulation millimetre-wave spectrometer equipped with a pyrolysis system for the production of unstable species. High-level ab initio calculations were performed to assist the analysis and to obtain reliable estimates for an extended set of spectroscopic quantities. We searched for propargylimine at 3 mm and 2 mm in the spectral survey of the quiescent giant molecular cloud G+0.693-0.027 located in the central molecular zone, close to the Galactic centre. Results. About 1000 rotational transitions have been recorded for the E- and Z-propargylimine, in the laboratory. These new data have enabled the determination of a very accurate set of spectroscopic parameters including rotational, quartic, and sextic centrifugal distortion constants. The improved spectral data allowed us to perform a successful search for this new imine in the G+0.693-0.027 molecular cloud. Eighteen lines of Z-propargylimine were detected at level >2.5σ, resulting in a column-density estimate of N = (0.24 ± 0.02) × 1014 cm−2. An upper limit was retrieved for the higher energy E isomer, which was not detected in the data. The fractional abundance (with respect to H2) derived for Z-propargylimine is 1.8 × 10−10. We discuss the possible formation routes by comparing the derived abundance with those measured in the source for possible chemical precursors.

The millimeter-wave spectrum and astronomical search for ethyl methyl sulfide.

Sulfur-containing molecules constitute only 8% of the molecules observed in the interstellar medium (ISM), in spite of the fact that sulfur has been shown to be an abundant element in the ISM. In order to understand the chemical behavior of the ISM and specific cases like the missing sulfur reservoir, a detailed chemical molecular composition in the ISM must be mapped out. Our goal is to investigate the rotational spectrum of ethyl methyl sulfide, CH3CH2SCH3, which ms to be a potential candidate for observation in the ISM since the simpler analogs, CH3SH and CH3CH2SH, have already been detected. Rotational spectrum of ethyl methyl sulfide has been observed before, but its experimental rotational parameters are not precise enough to allow its detection in the ISM. The rotational spectrum of ethyl methyl sulfide in the frequency range 72-116.5 GHz was measured using a broadband millimeter-wave spectrometer based on radio astronomy receivers with fast Fourier transform backends. The spectral searches and identification of the vibrational excited states of ethyl methyl sulfide was supported by high-level ab initio calculations on the harmonic and anharmonic force fields. The rotational spectra for the trans and gauche conformers of ethyl methyl sulfide was analyzed, and a total of 172 and 259 rotational transitions were observed for each one, respectively. The observation of A - E internal rotation splittings allowed the experimental determination of the V 3 hindered internal rotation barrier height for both trans and gauche species. In addition, the vibrational excited states, resulting from the lowest frequency vibrational mode ν 30 were identified for both conformers. The new experimental rotational parameters were employed to search for ethyl methyl sulfide in the warm and cold molecular clouds Orion KL, Sgr B2(N), B1-b and TMC-1, using the spectral surveys captured by IRAM 30 m at 3 mm and 2 mm.

Millimeter-wave emission spectrometer based on direct digital synthesis.

We present a millimeter-wave Fourier transform emission spectrometer whose design is based on the application of a direct digital synthesizer (DDS) up-converted into the Ku-band with subsequent frequency multiplication. The spectrometer covers the frequency range from 50 GHz to 110 GHz and from 150 GHz to 330 GHz. Owing to the fast frequency switching ability of the DDS in the spectrometer, the same radiation source is used both as a generator of short polarizing pulses and as a local oscillator for the heterodyne receiving system. Such a design provides intrinsically coherent reception that allows very long-term data averaging in the time domain, which improves considerably the maximum sensitivity of the spectrometer. The performances of the spectrometer including the data acquisition rate, the sensitivity, and the accuracy of line frequency measurements were tested on the rotational spectra of OCS, NH2CHO, and CH3CH2CN. We show that in the frequency range of 150-300 GHz, the maximum sensitivity of the spectrometer for a 10 min integration time is around 10-9 cm-1 (the minimal value of the absorption coefficient of detectable rotational transition) in the case of narrowband single frequency pulse excitation, and around 10-8 cm-1 in the case of broadband chirped-pulse excitation.

Rotational spectroscopy and astronomical search for glutaronitrile★.

Nitriles constitute almost 15% of the molecules observed in the interstellar medium (ISM), surprisingly only two dinitriles have been detected in the ISM so far. The lack of astronomical detections for dinitriles may be partly explained by the absence of laboratory rotational spectroscopic data. Our goal is to investigate the rotational spectrum of glutaronitrile, N≡C-CH2-CH2-CH2-C≡N, in order to allow its possible detection in the ISM. The rotational spectrum of glutaronitrile was measured using two different experimental setups. A Fourier transform microwave spectrometer was employed to observe the supersonic jet rotational spectrum of glutaronitrile between 6 and 20 GHz. In addition, the mmW spectrum was observed in the frequency range 72-116.5 GHz using a broadband millimetre-wave spectrometer based on radio astronomy receivers with fast Fourier transform backends. The spectral searches were supported by high-level ab initio calculations. A total of 111 rotational transitions with maximum values of J and Ka quantum numbers 54 and 18, respectively, were measured for the gg conformer of glutaronitrile. The analysis allowed us to accurately determine the rotational, nuclear quadrupole coupling, quartic and sextic centrifugal distortion constants. These rotational parameters were employed to search for glutaronitrile 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. Glutaronitrile was not detected, and the upper limits' column densities were derived. Those are a factor of 1.5 and 5 lower than those obtained for the total column densities of the analogous succinonitrile in Orion KL and Sgr B2, respectively.

Spectroscopy of a low global warming power refrigerant. Infrared and millimeter-wave spectra of trifluoroethene (HFO-1123) in the ground and some vibrational excited states

In the present work we carried out a combined rotational and ro-vibrational investigation on 1,1,2-trifluoroethene, a relevant unsaturated hydrofluoroolefin recently proposed as refrigerant in mixture with other halogenated compounds (like difluoromethane). By employing a frequency-modulation millimeter-wave spectrometer, the rotational spectra were recorded in the frequency ranges 80–96 GHz and 245–260 GHz for the ground and also the vibrationally excited states ν8=1,ν9=1,ν12=1,ν9=2,ν12=2, and ν9=ν12=1. In addition, the infrared spectra in the region of the ν6 band (centered at 929.8cm−1) were measured with a high-resolution Fourier transform spectrometer. The data coming from the detailed rotational and ro-vibrational assignments were combined in a global fit, taking into account also the ground state transitions available in the literature. From this analysis, a very accurate set of rotational and centrifugal distortion constants was determined for the ground state and for all the vibrationally excited states here investigated.

High-resolution millimeter-wave spectroscopy of CH2DCl: Paving the way for future astronomical observations of chloromethane isotopologues

Chloromethane is the only organochloride detected in space to date. Its recent observation towards the low-mass protostar IRAS 16293-2422 with ALMA offers a prompt for new laboratory studies of CH3Cl and its isotopologues. Here, we report the investigation of the rotational spectrum of monodeuterated chloromethane CH2DCl in the frequency region between 90 and 300 GHz. The measurements have been carried out with a frequency-modulation millimeter-wave spectrometer, arranged to perform saturation spectroscopy. From the analysis of hyperfine-resolved spectra of the two chlorine isotopologues CH2D35Cl and CH2D37Cl, consistent sets of accurate spectroscopic parameters have been obtained. This work provides reliable spectral predictions which can be used to guide radio-astronomical searches of CH2DCl in the interstellar medium and represents a solid base for future analyses of high-resolution infrared spectra of monodeuterated chloromethane.