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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.

We report the first high resolution spectroscopic study of the NH3–H2 van der Waals molecular complex. Three different experimental techniques, a molecular beam Fourier transform microwave spectrometer, a millimeter-wave intracavity jet OROTRON spectrometer, and a submillimeter-wave jet spectrometer with multipass cell, were used to detect pure rotational transitions of NH3–H2 in the wide frequency range from 39 to 230 GHz. Two nuclear spin species, (o)-NH3–(o)-H2 and (p)-NH3–(o)-H2, have been assigned as carriers of the observed lines on the basis of accompanying rovibrational calculations performed using the ab initio intermolecular potential energy surface (PES) of Maret et al. The experimental spectra were compared with the theoretical bound state results, thus providing a critical test of the quality of the NH3–H2 PES, which is a key issue for reliable computations of the collisional excitation and de-excitation of ammonia in the dense interstellar medium.

The rotational spectrum of the van der Waals NH3-N2 complex is studied in the frequency range of 112–130 GHz. The transitions are measured in a cold molecular beam with an intracavity spectrometer based on an orotron. A total of six new transitions of different spin modifications of the complex are recorded. Molecular parameters of the K = 0 ground state are determined for the orthoNH3-orthoN2 modification.

The rotational spectrum of the weakly bound Kr-CO molecular complex formed in a pulsed molecular jet has been measured in the frequency range 112–150 GHz on an intracavity orotron-based spectrometer. The measured b-type transitions include the R branch of the band K = 1-0 with the rotational numbers J from 16 to 25 and the P branch of the band K = 2-1 with the rotational numbers J from 13 to 17. For the K = 1-0 band, we succeeded in recording transitions in complexes that consist of all stable Kr isotopes, i.e., 84Kr-CO, 86Kr-CO, 82Kr-CO, 83Kr-CO, and 80Kr-CO. For the K = 2-1 band, we observed transitions in the two most abundant isotopologues, 84Kr-CO and 86Kr-CO. The obtained data were used to determine the rotational and centrifugal constants of the Kr-CO complex.

The pure rotational spectrum of the Ne–CO van der Waals complex has been measured in the frequency range of 208–230 GHz by using the Cologne supersonic jet spectrometer for terahertz applications (SuJeSTA). Eleven new transitions were assigned as belonging to two R- and two Q-branches of the K = 2–1 subband detected for the first time in the ground vibrational state of CO (νCO = 0). Improved molecular parameters of the Ne–CO complex were obtained which allowed for a sensitive test of the available intermolecular potential energy surfaces of the Ne–CO system.

A van der Waals complex that consists of a deuterium molecule in the ortho state and a carbon monoxide molecule, CO-ortho-D2, was studied in the frequency range 85–130 GHz with the help of an intracavity orotron-based spectrometer. Nine new lines, which correspond to rotational transitions and belong to the R and Q branches, were measured and identified. The positions of the rotational energy levels of CO-ortho-D2 were refined by comparative analysis of the transition frequencies measured in this work and previously reported microwave and infrared data.

Van der Waals complexes consisting of helium atoms and carbon monoxide molecules, He-12C16O, He-13C16O, He-12C18O, and He-13C18O are studied in the frequency range 110–140 GHz on an intracavity orotron-based spectrometer. Ten new lines, which correspond to rotational transitions and transitions to the bending vibration of the complex, are detected and identified as lines belonging to the R and P branches. The positions of the energy levels of isotopologue of the He-CO complex are refined by joint analysis of both the transition frequencies measured in this study and previously published microwave and infrared data. Isotopic dependences of the positions of the He-CO energy levels are obtained. These results can serve as the starting point for studying small helium clusters with embedded CO molecules.

Rotational transitions of the CO–N 2 van der Waals complex have been measured using the intracavity OROTRON jet spectrometer in the frequency range of 83–133 GHz. For the CO– ortho N 2 spin modification, the observed and assigned 21 rotational transitions belong to the Q - and P -branches of the K =1–0 subband. They complete the previous observation of the corresponding R -branch transitions. In the case of the less abundant form, CO– para N 2 , a new K =1 state, representing simultaneous rotation of both monomers, was detected for the first time. A total of 31 rotational transitions of CO– para N 2 were assigned to two subbands connecting this new K =1 state with already known lower K =0 and 1 states. The assignments relied in part on energy level differences obtained from precise microwave data. The origin of the newly observed state was determined to be 3.41 cm −1 relative to the K =0 ground state of CO– para N 2 . The analysis yielded rotational parameters, centrifugal distortion parameters and nuclear quadrupole coupling constants due to the presence of two equivalent 14 N nuclei for both CO– ortho N 2 and CO– para N 2 .

The b -type rotational transitions of the van der Waals complex, Ne–CO have been measured using the intracavity OROTRON jet spectrometer in the frequency range of 80–115 GHz. The high sensitivity of this technique enabled us to detect all three Ne isotopic modifications of the complex, 20 Ne–CO, 22 Ne–CO, and 21 Ne–CO in natural abundance. The observed and assigned transitions belong to the Q -branch of the K = 1–0 subband and include also R (0) and P (2) lines. The newly obtained data were analysed together with previously observed millimeter-wave b -type and microwave a -type rotational transitions.

The bending vibration of the CO–N 2 complex has been investigated in the millimeter wave range from 130 to 155 GHz using an intracavity OROTRON jet spectrometer. Six transitions, P (2), P (1), R (0), R (1), R (2), and R (3) from the K =0 ground state to the K =0 bending state of the ortho N 2 spin modification were measured and analyzed. Nuclear quadrupole structure due to the presence of two equivalent 14 N nuclei was partly resolved and analyzed to give information about the angular anisotropy of the interaction potential. The frequency of the bending vibration was determined to be 139892.459(35) MHz. The nuclear quadrupole coupling constant for the K =0 bending state of CO– ortho N 2 was obtained for the first time to be χ aa =−0.768(43) MHz . The different value and sign of this constant from the one in the K =0 ground state, (χ aa =+0.19641 MHz ) suggests that the orientation and motion of the N 2 subunit are very different in these two states.

The pure rotational spectrum of the van der Waals complex, CH 4 –CO, has been measured using the intracavity OROTRON jet spectrometer in the frequency range of 116–146 GHz. The newly observed and assigned transitions belong to the R -branch with J numbers from 9 to 16 of the K = 1–0 sub-band. This series is a continuation to higher J -values of transitions correlating with the rotationless j M = 0 state ( A symmetry state) of free methane observed previously at lower frequencies [C. Xia, K.A. Walker, A.R.W. Mckellar, J. Chem. Phys. 114 (2001) 4824]. Both data sets were analyzed together with known infrared and microwave transitions in order to determine the molecular parameters of the of CH 4 –CO complex in the A state. The observed millimeter-wave spectrum shows numerous additional transitions which very likely belong to CH 4 –CO composed of methane in the F ( j M = 1) and E ( j M = 2) symmetry states, but these have not yet been assigned.

A highly sensitive intracavity millimeter-wave spectrometer was developed for the investigation of the absorption spectra of van der Waals complexes in a supersonic jet. The key element of the spectrometer is a tunable oscillator, called OROTRON, which generates the millimeter-wave radiation through the interaction of an electron beam with the electromagnetic field of a high quality (Q≈104) Fabry–Perot resonant cavity. This cavity consists of a movable spherical mirror and a fixed planar mirror with the periodic structure imprinted on its surface. The electron beam moves along the periodic structure of the plane mirror. This part separated from the rest of the resonator by a mica foil is kept under ultrahigh vacuum conditions. The molecular jet is injected by a pulsed valve into the other part of the resonator. The absorption in the jet is sensitively detected by measuring the electric current in a special collector circuit of the OROTRON. The spectral purity of the OROTRON radiation is 10–15 kHz providin...

The rotational spectra of the NH 3 –D 2 and ND 3 –H 2 van der Waals complexes have been observed in a supersonic molecular jet for the first time. The OROTRON intracavity spectrometer was used to detect pure rotational transitions in the frequency range from 75 to 120 GHz. The search of the spectral lines was based on the initial observation of the main isotopic species of the NH3−H2. The measured transition frequencies including hyperfine splitting were analyzed in order to determine the energy levels, molecular parameters and structure of the ortho ND 3 − ortho H 2 and ortho NH 3 − para D 2 complexes.

A recently developed highly sensitive intracavity millimeter wave (MMW) spectrometer has been applied for spectroscopy of molecules in excited vibrational states. The spectrometer utilizes an Orotron oscillator as the tunable, coherent source of radiation from 90 to 160 GHz. A gas cell is placed into a high quality ( Q ≈10 4 ) Fabry–Perot resonator of Orotron, and the absorption signal is detected from the variation of the Orotron electron current in a collector circuit. The spectrometer combines a wide spectral range with Doppler spectral resolution without any phase or frequency lock techniques and achieves the sensitivity in absorption of (3–5)×10 −10 cm −1 . The measurements are presented for rotational and ro-vibrational transitions of SiH 4 in the ν 2 / ν 4 vibrational dyad and high- J pure inversion spectrum of ND 3 in the v 2 =1 vibrational state. Qualitative description of MMW ν 2 / ν 4 dyad spectrum of SiH 4 and analysis of available microwave (MW) data on the pure inversion spectrum of ND 3 in v 2 =1 state are also given.

A portion of the CO dimer millimeter wave absorption spectrum has been studied by using our highly sensitive intracavity-jet OROTRON spectrometer in the frequency range from 131 to 174 GHz. By varying the CO concentration in the Ne/CO gas mixture feeding the supersonic jet expansion, the effective temperature of the beam could be changed, revealing a correlation between the observed line intensity and the relative energy of the respective lower state energy levels. Using this temperature dependence and the technique of combination differences together with the data from the infrared study of Brookes and McKellar [J. Chem. Phys. 111, 7321 (1999)], out of over 200 observed transitions, a total of 19 lines could be assigned. All assigned millimeter-wave transitions are tunneling transitions. They belong to four subbands, which connect seven lower energy levels with A+ symmetry to ten previously unknown upper energy levels with A− symmetry. The A+ and A− separation signifies the tunneling splitting of the CO ...

For the first time, millimeter wave absorption spectra of the van der Waals complexes 3He–CO and 4He–CO were detected in a supersonic jet. Altogether four rotational transitions of 3He–CO and six rotational transitions of 4He–CO were recorded between 110 GHz and 127 GHz with an intracavity spectrometer based on the millimeter wave generator, called OROTRON. The obtained results were included in a global fit together with previously known data enabling a more precise determination of the energy levels of the 3He–CO and 4He–CO complexes. In extremely cold, dark, and dense interstellar clouds the He–CO complex may have astrophysical relevance.

Microwave and millimeter wave transitions of the CO–N2 complex were investigated using three different instruments, namely, a pulsed molecular beam Fourier transform microwave spectrometer in the frequency region from 4 to 26 GHz, a microwave-millimeter wave double resonance spectrometer in the frequency regions from 8 to 18 GHz for the microwave and 107–118 GHz for the millimeter wave range, and an OROTRON spectrometer in the frequency range from 107 to 132 GHz. Both a- and b-type transitions associated with the ground-state K=0 levels and the lower K=1 levels of the ortho-N2 states, and with rotational quantum number J up to 19, were measured and analyzed. Nuclear quadrupole hyperfine splittings due to the presence of two equivalent 14N nuclei were resolved and analyzed to give additional information about the angular anisotropy of the interaction potential. The nuclear quadrupole coupling constants obtained are χaa=0.196 41(52) MHz for K=0 levels, and χaa=−1.0391(17) MHz, χbb=0.0633(17) MHz for the low...

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.

Rotational transitions of the CO–H2 van der Waals complex have been measured between 108 and 125 GHz in a supersonic jet. Three absorption lines were recorded and assigned as belonging to CO–paraH2 with a new highly sensitive intracavity spectrometer based on the millimeter wave generator, called OROTRON. The results provide confirmation of the recent infrared data of McKellar at 4.7 μm, enabling a more precise determination of the energies of the rotational levels with different parity in the vibrational ground state. The measured millimeter wave transitions provide precise frequencies for an astronomical search of CO–paraH2.

Highly sensitive millimeter-wave spectrometer based on tunable coherent source—orotron is proposed for detection of molecular compounds in the air and water vapor by observation of their rotational spectra in frequency region 90–150 GHz. High sensitivity of measurements (2–3)×10−10 cm−1 which gives the detection limit better than 1 ppm for wide class of molecules is achieved by the placement of investigated gas into a high quality (Q≈104) orotron Fabry–Perot resonator. The absorption signal is measured simply from variation of orotron current in the collector circuit. The narrow spectral width of orotron radiation (15 kHz) provides Doppler resolution of spectral lines and high selectivity of analysis respectively without any locking by external frequency standard. The spectrometer has relatively simple operation principles taking account its universality. At the first step four compounds, namely methanol, acetone, carbonyl sulfide and carbon monoxide, have been measured in mixtures with water vapor or air.

A description is presented for two unconventional highly sensitive spectrometers operating in the decimeter‐wave region (90–450 MHz) and millimeter‐wave region (90–150 GHz), respectively. In both cases a resonant cavity is used as an absorption cell. Either design combines high sensitivity with high resolution and wide spectral range. The radio frequency spectrometer allows measuring of extremely low absorption quantity 3×10−12 cm−1 in combination with high spectral resolution of order 1 kHz with the radio frequency–microwave double resonance method. The gas cell is a coaxial cavity (Q≊103) with a diameter of 40 cm and length about a wavelength. The millimeter‐wave spectrometer utilizes an orotron oscillator as the tunable, coherent source of radiation from 90 to 150 GHz. A gas cell is placed into a high quality (Q≊104) Fabry–Perot resonator of the orotron, and the absorption signal is detected by variation of the orotron electron current in the collector circuit. The sensitivity limit of (2–5)×10−10 cm−1...

The design and operation of a gas millimeter-wave spectrometer based on a tunable generator orotron are presented. The absorption cell occupies a part of the high quality (Q approximately equals 10 4 ) orotron Fabry-Perot cavity. The limit of sensitivity (gamma) min approximately equals (3- 5)X 10 -10 cm -1 has been achieved with source frequency modulation at the output band of a receiver of 1 Hz. The narrow spectral width of the orotron radiation (10 - 15 kHz without locking) provides the Doppler resolution of spectral lines.

For the first time two rotational transitions of the CO–orthoD2 van der Waals molecular complex have been recorded in a supersonic jet and assigned to the two R-branch transitions, R(1) (J,j,l)=2,1,1←1,0,1 112 806.515(50) MHz, R(2)=3,1,2,←2,0,2 119 746.484(50) MHz. These transitions were detected with the highly sensitive intracavity spectrometer based on the millimeter wave generator, called OROTRON. Their measured frequencies are in close agreement with the frequency positions predicted from the infrared spectrum, which accompanies the fundamental band of CO in the 4.7 μm region, and which has been published recently by McKellar [J. Chem. Phys. 112, 9282 (2000)]. The millimeter wave transitions will allow a precise determination of the rotational levels with different parity in the vibrational vCO=0 ground state.