Low frequency microwave spectroscopy ( < 10 GHz) is ideal for studies of large molecular systems including higher order molecular complexes. The cold rotational temperature of a pulsed jet makes detections in this region highly attractive for these larger molecular systems with small rotational constants. Here, we report on the construction and initial benchmarking results for a new 2.0-6.0 GHz CP-FTMW spectrometer, similar in design to the 2.0-8.0 GHz spectrometer designed in Brooks Pate’s group at the University of VirginiaC. Perez, S. Lobsiger, N. A. Seifert, D. P. Zaleski, B. Temelso, G. C. Shields, Z. Kisiel, B. H. Pate, Chem. Phys. Lett., 2013, 571, 1-15. that takes advantage of numerous improvements in solid-state microwave devices and high-speed digitizers.
In addition to details and analysis of the new instrumental design, comparisons to the previous generation 7.5-18.0 GHz spectrometer at the University of Alberta will be presented using the microwave spectrum of methyl lactate as a benchmark. Finally, initial results for several novel molecular systems studied using this new spectrometer, including the tetramer of 2-fluoroethanol, will be presented.

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C. Perez, S. Lobsiger, N. A. Seifert, D. P. Zaleski, B. Temelso, G. C. Shields, Z. Kisiel, B. H. Pate, Chem. Phys. Lett., 2013, 571, 1-15.,

In the past decade, astrochemistry has seen an increase in interest. As higher throughput and increased resolution radio astronomy facilities come online, faster laboratory instrumentation that directly covers the frequency ranges of these facilities is needed. The 18-26 GHz region is of interest astronomically as many cold organic molecules have their peak intensity in this region. We present here a new segmented chirped pulse Fourier transform microwave (CP-FTMW) spectrometer operating between 18-26 GHz. Using state-of-the-art digital electronics and the segmented approach[1], this design has the potential to be faster and cheaper than the previously presented broadband design. Characterization of the instrument using OCS will be presented, along with a comparison to the previously built and optimized 18-26 CP-FTMW built at the University of Virginia. It will be coupled with a discharge nozzle[2], and its applications to astrochemistry will be explored in this talk. [1] Neill, J.L., Harris, B.J., Steber, A.L., Douglass, K.O., Plusquellic, D.F., Pate, B.H. Opt. Express, 21, 19743-19749, 2013. [2] McCarthy, M.C., Chen, W., Travers, M.J., Thaddeus, P. Astrophys. J. Suppl. Ser., 129, 611-623 , 2000.

A highly integrated supersonic-jet Fourier-transform microwave spectrometer of coaxially oriented beam-resonator arrangement (COBRA) type, covering 2-20GHz, has been recently built at Chongqing University, China. Built up almost entirely in an NI PXIe chassis, we take the advantage of the NI PXIe-5451 Dual-channel arbitrary waveform generator and the PXIe-5654 RF signal generator to create a spectrometer with wobbling capacity for fast resonator tuning. Based on the I/Q modulation, associate with PXI control and sequence boards built at the Leibniz Universitat Hannover, the design of the spectrometer is much simpler and very compact. The Fabry–Pérot resonator is semi-confocal with a spherical reflector of 630 mm diameter and a radius of 900 mm curvature and one circulator plate reflector of 630 mm diameter. The vacuum is effectuated by a three-stage mechanical (two-stage rotary vane and roots booster) pump at the fore line of a DN630 ISO-F 20000 L/s oil-diffusion pump. The supersonic-jet expansion is pulsed by a general valve Series 9 solenoid valve which is controlled by a general valve IOTA one driver governed by the experiment-sequence generation. First molecular examples to illustrate the performance of the new setup will include OCS and CF₃CHFCl.

l0pt Figure Microwave spectroscopy has been restricted to the investigation of small molecules in the last years. However, with the advent of FTMW and CP-FTMW spectroscopies coupled with laser vaporization techniques it has turned into a very competitive methodology in the studies of moderate-size molecules. In particular, the studies of relatively large molecular aggregatesT. Tang, Y. Xu, A. R. W. McKellar and W. Jäger, Science 29, 297, 2002.^, C. Prez, M. T. Muckle, D. P. Zaleski, N. A. Seifert, B. Temelso, G. H. Shields, Z. Kisiel and B. H. Pate, Science 336, 897, 2012.aI. Uriarte, C. Prez, E. Caballero-Mancebo, F. J. Basterretxea, A. Lesarri, J. A. Fernndez and E. J. Cocinero Chem. Eur. J. in press, 2017.a

The conformational energy differences of various chemicals have been measured using chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. The hypothesis is that the relative intensities measured in a pulsed-jet instrument are proportional to the conformer populations present before the expansion occurs. Therefore, by measuring the relative intensities in a CP-FTMW spectrum, we aim to determine the relative energy difference between conformers. Experimentally, pulsed-jet CP-FTMW data will be compared to energy differences reported in the literature and to room-temperature CP-FTMW data acquired at Coker College. Results from ab initio calculations will also be used for comparison.

Over the last few years, we have been working to improve the AUTOFIT programSeifert, N.A., Finneran, I.A., Perez, C., Zaleski, D.P., Neill, J.L., Steber, A.L., Suenram, R.D., Lesarri, A., Shipman, S.T., Pate, B.H., J. Mol. Spec. 312, 13-21 (2015)nd extend it to work on more complex spectra, especially spectra collected near room temperature. In this talk, we will discuss the problem of spectral complexity and the challenges it poses for moving to increasingly complicated systems. This will be highlighted by the cases of methoxyethanol, in which AUTOFIT was able to easily extract contributions from the ground state and four vibrationally excited states, and ethoxyethanol, in which AUTOFIT had difficulty identifying more than the ground vibrational state without the assistance of additional double resonance measurements.

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Footnotes:

Seifert, N.A., Finneran, I.A., Perez, C., Zaleski, D.P., Neill, J.L., Steber, A.L., Suenram, R.D., Lesarri, A., Shipman, S.T., Pate, B.H., J. Mol. Spec. 312, 13-21 (2015)a

Two new laboratory heterodyne emission spectrometers are presented that are currently used for high-resolution rotational spectroscopy of complex organic molecules. The room temperature heterodyne receiver operating between 80-110 GHz, as well as the SIS heterodyne receiver operating between 270-370 GHz allow access to two very important frequency regimes, coinciding with Bands 3 and 7 of the ALMA (Atacama Large Millimeter Array) telescope. Taking advantage of recent progresses in the field of mm/submm technology, we build these two spectrometers using an XFFFTS (eXtended Fast Fourier Transform Spectrometer) for spectral acquisition. The instantaneous bandwidth is 2.5 GHz in a single sideband, spread over 32768 channels. Thus, the spectral resolution is about 76 kHz per channel and thus comparable to high resolution spectra from telescopes. Both receivers are operated in double sideband mode resulting in a total instantaneous bandwidth of 5 GHz. The system performances, in particular the noise temperatures and stabilities are presented. Proof-of-concept is demonstrated by showing spectra of methyl cyanide obtained with both spectrometers. While the transition frequencies for this molecule are very well known, intensities of those transitions can also be determined with high accuracy using our new instruments. This additional information shall be exploited in future measurements to improve spectral predictions for astronomical observations. Other future prospects concern the study of more complex organic species, such as ethyl cyanide. These aspects of the new instruments as well as limitations of the two distinct receivers will be discussed.

Detecting molecules of astrophysical interest in the interstellar medium strongly relies on precise spectroscopic data from the laboratory. In recent years, the advancement of the chirped-pulse technique has added many more options available to choose from. The Cologne emission spectrometer is an additional path to molecular spectroscopy. It allows to record instantaneously broad band spectra with calibrated intensities. Here we present a comparison of both methods: The Cologne chirped-pulse spectrometer as well as the Cologne emission spectrometer both cover the frequency range of 75-110 GHz, consistent with the ALMA Band 3 receivers. High sensitive heterodyne receivers with very low noise temperature amplifiers are used with a typical bandwidth of 2.5 GHz in a single sideband. Additionally the chirped-pulse spectrometer contains a high power amplifier of 200 mW for the excitation of molecules. Room temperature spectra of methyl cyanide and comparison of key features, such as measurement time, sensitivity, limitations and commonalities are shown in respect to identification of complex molecules of astrophysical importance. In addition, future developments for both setups will be discussed.

Laboratory spectroscopy, especially at THz and mm-wave ranges require the advances in instrumentation techniques to provide high resolution of the recorded spectra with precise frequency measurement that facilitates the mathematical treatment. We report the first implementation of a Schottky heterodyne receiver, operating at room temperature and covering the range between 530 and 590 GHz, for molecular laboratory spectroscopy. A 530-590 GHz non-cryogenic Schottky solid-state receiverJ. Treuttel, L. Gatilova, A. Maestrini et al., 2016, IEEE Trans. Terahertz Science and Tech., 6, 148-155.as designed at LERMA, Observatoire de Paris and fabricated in partnership with LPN- CNRS (Laboratoire de Photonique et de Nanostructures), and was initially developed for ESA Jupiter Icy Moons Explorer (JUICE), intended to observe Jupiter and its icy moon atmospheres. It is based on a sub-harmonic Schottky diode mixer, designed and fabricated at LERMA-LPN, pumped by a Local Oscillator (LO), consisting of a frequency Amplifier/Multiplier chains (AMCs) from RPG (Radiometer Physics GmBh). The performance of the receiver was demonstrated by absorption spectroscopy of CH₃CH₂CN with Lille's fast-scan DDS spectrometer. A series of test measurements showed the receiver's good sensitivity, stability and frequency accuracy comparable to those of 4K QMC bolometers, thus making room-temperature Schottky receiver a competitive alternative to 4K QMC bolometers to laboratory spectroscopy applications. We will present the first results with such a combination of a compact room temperature Schottky heterodyne receiver and a fast-scan DDS spectrometer. This work was funded by the French ANR under the Contract No. ANR-13-BS05-0008-02 IMOLABS.

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J. Treuttel, L. Gatilova, A. Maestrini et al., 2016, IEEE Trans. Terahertz Science and Tech., 6, 148-155.w

A new generation of CMOS circuits operating at 89-104 GHz with improved output power and pulse switch isolation have enhanced the performance of the miniaturized pulsed-echo Fourier transform spectrometer under development for planetary exploration at the Jet Propulsion laboratory. Additional progress has been made by creating a waveguide-fed structure for the novel planar coupler design. This structure has enabled characterization of each component in the system and enabled spectroscopy to be done with conventional millimeter hardware that enables (1) direct comparisons to the CMOS components, (2) enhanced bandwidth of 74-109 GHz, and (3) amplification of the transmitter prior to cavity injection. We have now demonstrated the technique with room temperature detections on multiple species including N₂O, OCS, CH₃CN, CH₃OH, CH₃NH₂, CH₃CHO, CH₃Cl, HDO, D₂O, CH₃CH₂CN and CH₃CH₂OH. Of particular interest to spectroscopic work in the millimeter range is the ongoing incorporation of a ∆Σ radio-frequency source into the millimeter-wave lock-loop - this has improved the phase-noise of the tunable CMOS transceiver to better than the room-temperature Doppler limit and provides a promising source for general use that may replace the high end microwave synthesizers. We are in the process of building a functional interface to the various subsystems. We will present a trade-space study to determine the optimal operating conditions of the pulse-echo system.

Plasmas used for the manufacturing of semiconductor devices are similar in pressure and temperature to those used in the laboratory for the study of astrophysical species in the submillimeter (SMM) spectral region. The methods and technology developed in the SMM for these laboratory studies are directly applicable for diagnostic measurements in the semiconductor manufacturing industry. Many of the molecular neutrals, radicals, and ions present in processing plasmas have been studied and their spectra have been cataloged or are in the literature. In this work, a continuous wave, intensity calibrated SMM absorption spectrometer was developed as a remote sensor of gas and plasma species. A major advantage of intensity calibrated rotational absorption spectroscopy is its ability to determine absolute concentrations and temperatures of plasma species from first principles without altering the plasma environment. An important part of this work was the design of the optical components which couple 500−750 GHz radiation through a commercial inductively coupled plasma chamber. The measurement of transmission spectra was simultaneously fit for background and absorption signal. The measured absorption was used to calculate absolute densities and temperatures of polar species. Measurements for CHF₃, CF₂, FCN, HCN, and CN made in a CF₄/CHF₃/N₂ plasma will be presented. Temperature equilibrium among species will be shown and the common temperature is leveraged to obtain accurate density measurements for simultaneously observed species. The densities and temperatures of plasma species are studied as a function of plasma parameters, including flow rate, pressure, and discharge power.