A laboratory heterodyne emission spectrometer at submillimeter wavelengths.

We present first results on a newly built broadband emission spectrometer for the laboratory making use of a double sideband (DSB) heterodyne receiver. The new spectrometer is perfectly suited for high-resolution emission spectroscopy of molecules of astrophysical importance. The current SIS receiver operates at RF frequencies between 270 and 390 GHz, coincident with Band 7 of the ALMA telescope. The instantaneous bandwidth is 5 GHz (DSB). In this work the full spectrometer and its components are described. Its performance, in particular its sensitivity, stability, reproducibility and systematic errors, is characterized in detail. For this purpose very broad band emission spectra of methyl cyanide have been recorded and compared to theoretical spectra. Isotopic variants are found in natural abundance and features attributed to vibrationally excited species are all recorded in the same spectrum. The performance of the new spectrometer is compared extensively to that of a traditional FM-absorption spectrometer and to recent versions of chirped-pulse spectrometers operated in the mm-wave regime. Further applications and future advancements of the current instrument are discussed.

Terahertz and far-infrared synchrotron spectroscopy and global modeling of methyl mercaptan, CH3(32)SH.

In this work, terahertz and Fourier transform far-infrared (FTFIR) synchrotron spectra of methyl mercaptan, CH(3)SH, have been investigated in order to provide new laboratory information for enhanced observations of this species in interstellar molecular clouds and star-forming regions. Like its methanol cousin, methyl mercaptan has particularly rich spectra associated with its large-amplitude internal rotation that extend throughout the THz and FIR regions. We have recorded new spectra for CH(3)SH from 1.1-1.5 and 1.790-1.808 THz at the University of Cologne as well as high-resolution FTFIR synchrotron spectra from 50-550 cm(-1) at 0.001 cm(-1) resolution on the far-IR beam-line at the Canadian Light Source. Assignments are reported for rotational quantum numbers up to J ≈ 40 and K ≈ 15, and torsional states up to v(t) = 2 for the THz measurements and v(t) = 3 for the FTFIR observations. The THz and FTFIR measurements together with literature results have been combined in a global analysis of a dataset comprising a total of 1725 microwave and THz frequencies together with ~18000 FTFIR transitions, ranging up to v(t) = 2 and J(max) = 30 for MW∕THz and 40 for FTFIR. The global fit employs 78 torsion-rotation parameters and has achieved a weighted standard deviation of ~1.1. A prediction list (v(t) ≤ 2, J ≤ 45 and K ≤ 20) has been generated from the model giving essentially complete coverage of observable CH(3)(32)SH transitions within the bandwidths of major new astronomical facilities such as HIFI (Heterodyne Instrument for the Far Infrared) on the Herschel Space Observatory, ALMA (Atacama Large Millimeter Array), SOFIA (Stratospheric Observatory For Infrared Astronomy) and APEX (Atacama Pathfinder Experiment) to close to spectroscopic accuracy.

Dichroic filters to protect milliwatt far-infrared detectors from megawatt ECRH radiation.

Dichroic filters have been used to shield effectively the far infrared (FIR) detectors at the interferometer/polarimeter on TEXTOR. The filters consist of metal foils with regular holes, the hole diameter, the mutual spacing and the thickness of the foils are chosen to transmit radiation at the design frequency with transmission >90%. The attenuation at the low frequency end of the bandpass filter is about 30 dB per octave, the high frequency transmission is between 20% and 40%. The filters have been used to block the stray radiation from the megawatt microwave heating beam to the detectors of the FIR interferometer, operating with power on the detector in the milliwatt range. If required, the low frequency attenuation can be still enhanced, without compromising the transmission in the passband. The FIR interferometer used for plasma density and position control is no longer disturbed by electromagnetic waves used for plasma heating.

Application of superlattice multipliers for high-resolution terahertz spectroscopy.

Frequency multipliers based on superlattice (SL) devices as nonlinear elements have been developed as radiation sources for a terahertz (THz) laboratory spectrometer. Input frequencies of 100 and 250 GHz from backward wave oscillators have been multiplied up to the 11th harmonic, producing usable frequencies up to 2.7 THz. Even at these high frequencies the output power is sufficient for laboratory spectroscopy. Comparisons to conventional high-resolution microwave spectroscopy methods reveal several superior features of this new device such as very high line frequency accuracies, broadband tunability, high output power levels at odd harmonics of the input frequency up to high orders, and a robust applicability.

Rotational spectroscopy of the isotopic species of silicon monosulfide, SiS.

Pure rotational transitions of silicon monosulfide ((28)Si(32)S) and its rare isotopic species have been observed in their ground as well as vibrationally excited states by employing Fourier transform microwave (FTMW) spectroscopy of a supersonic molecular beam at centimetre wavelengths (13-37 GHz) and by using long-path absorption spectroscopy at millimetre and submillimetre wavelengths (127-925 GHz). The latter measurements include 91 transition frequencies for (28)Si(32)S, (28)Si(33)S, (28)Si(34)S, (29)Si(32)S and (30)Si(32)S in upsilon = 0, as well as 5 lines for (28)Si(32)S in upsilon = 1, with rotational quantum numbers J''< or = 52. The centimetre-wave measurements include more than 300 newly recorded lines. Together with previous data they result in almost 600 transitions (J'' = 0 and 1) from all twelve possible isotopic species, including (29)Si(36)S and (30)Si(36)S, which have fractional abundances of about 7 x 10(-6) and 4.5 x 10(-6), respectively. Rotational transitions were observed from upsilon = 0 for the least abundant isotopic species to as high as upsilon = 51 for the main species. Owing to the high spectral resolution of the FTMW spectrometer, hyperfine structure from the nuclear electric quadrupole moment of (33)S was resolved for species containing this isotope, as was much smaller nuclear spin-rotation splitting for isotopic species involving (29)Si. By combining the measurements here with previously published microwave and infrared data in one global fit, an improved set of spectroscopic parameters for SiS has been derived which include several terms describing the breakdown of the Born-Oppenheimer approximation. With this parameter set, highly accurate rotational frequencies for this important astronomical molecule can now be predicted well into the terahertz region.

Submillimeter-Wave Spectroscopy of Phosphaalkynes: HCCCP, NCCP, HCP, and DCP.

The submillimeter-wave rotational spectra of the unstable phosphorus-bearing molecules HCCCP (phosphabutadiyne) and NCCP (C-cyanophosphaethyne) have been investigated in selected frequency regions between 490 and 815 GHz using the Cologne Terahertz Spectrometer. Both molecules were studied in their ground vibrational states. Additionally, vibrational satellites within the bending states v(4) = 1 and v(5) = 1 were recorded for NCCP. Furthermore, the ground state rotational spectra of the (13)C and (15)N isotopomers of NCCP were detected in natural abundance. The new measurements allowed us to evaluate the sextic centrifugal distortion constants for each isotopomer and vibrational state investigated. The pyrolysis reactions, through which HCCCP and NCCP were produced in situ, also yielded phosphaethyne, HCP, as a by-product. Some transitions of HCP and DCP were recorded in their ground vibrational states along with v(2) = 1 vibrational satellites of the former. Copyright 2001 Academic Press.

Sub-Doppler Measurements of the Rotational Spectrum of (13)C(16)O.

The five lowest J rotational transitions of (13)C(16)O have been measured by saturation-dip spectroscopy to an accuracy of about 2 kHz, employing phase-stabilized backward-wave oscillators (BWOs). These highly precise measurements cover the transitions from J = 2 <-- 1 to J = 6 <-- 5 with frequencies ranging from 220 to 661 GHz. For each of the five observed rotational transitions, the narrow linewidths of the saturation dips (about 20 kHz) permitted the resolution of the hyperfine splitting for the first time. This splitting is caused by the (13)C-nuclear spin-rotation interaction yielding a value for the nuclear spin-rotation coupling constant of C(I)((13)C(16)O). If combined with the beam measurements (C(I)((13)C(16)O) = 32.63(10) kHz), a slight J-dependence of the spin-rotation coupling constant can be determined (C(J) = 30 +/- 13 Hz). In addition, we have measured in the Doppler-limited mode several higher J rotational line positions of (13)C(16)O up to 991 GHz with an accuracy of 5 kHz. The two line positions (J = 12 <-- 11 and J = 14 <-- 13) were recorded by multiplying BWO frequency with an accuracy of 100 kHz. The rotational transitions J = 17 <-- 16 and J = 18 <-- 17 were measured with an accuracy between 15 and 25 kHz by using the Cologne sideband spectrometer for terahertz applications COSSTA. Copyright 2000 Academic Press.

Submillimeter Detection of the van der Waals Stretching Vibration of the Ar-CO Complex.

With the Cologne submillimeter-wave supersonic jet spectrometer, we extended molecular jet spectroscopy with backward wave oscillators up to frequencies of about 600 GHz. For the first time, the van der Waals stretching vibration of the Ar-CO molecular complex was detected in direct absorption. We measured 13 ro-vibrational transitions (Kvstretch = 1 <-- 0, Ka = 0 <-- 0) in the frequency range from 528 to 600 GHz and additionally the two R(3) K doublet (Ka = 4 <-- 3) pure rotational transitions at 447 GHz with an accuracy of about 200 kHz. The ro-vibrational transitions were assigned and fitted within experimental accuracy to a simple Hamiltonian taking into account the Coriolis interaction between the stretching and bending states, i.e., between vstretch = 1, Ka = 0, and vbend = 1, Ka = 1. The intensity of the transitions in the van der Waals stretching mode was estimated to be a factor of 5-10 less than that in the bending mode of Ar-CO. Copyright 1999 Academic Press.

Transmission features of frequency-selective components in the far infrared determined by terahertz time-domain spectroscopy.

Transmission and phase-shift characteristics of dichroic high-pass filters with cutoff frequencies as high as 1.11 THz and of a cross-shaped grid bandpass filter with a resonance frequency of 280 GHz were measured with an electro-optic sampling terahertz time-domain spectrometer operating between 0.1 and 2 THz. Good agreement with transmission theories is found. We also compare the transmission performance of cascaded dichroic filters with that of cross-shaped grid bandpass filters. Both types of bandpass filter permit frequency-selective ultrafast experiments in the far-infrared spectral region. In the millimeter and the submillimeter wavelength regions, which are difficult to access by conventional means, knowledge of the frequency response of frequency-selective components is important for applications in frequency mixing, multiplying, and multiplexing in quasi-optical systems.

Submillimeter-Wave Absorption Spectroscopy of the Ar-CO Complex: Detection of the van der Waals Bending Vibration

Van der Waals bending rovibrational transitions of the Ar-CO complex were observed between 308 and 383 GHz using submillimeter-wave absorption spectroscopy in a pulsed supersonic jet. The submillimeter radiation was generated by a phase-stabilized backward wave oscillator source. Fourteen transitions of the P and R branch of the bending vibration were measured with an accuracy of about 100 kHz. The frequencies were fitted using effective molecular parameters including the band origin and the rotational constants for the ground state and for the excited bending vibrational state.