Search

A millimeter-wave intracavity OROTRON spectrometer in combination with a pulsed supersonic pin-hole jet expansion has been used to record a new subband of the CO–N 2 weakly bound van der Waals complex in the 100–150 GHz region. Seven lines were assigned to the K = 0–0, ( j CO , j N2 ) = (2, 0)–(1, 0) “hot band” transitions to a thus far unobserved K = 0 state at 9.336 cm −1 above the ground state. This is the highest in energy van der Waals mode detected so far, and this mode may be interpreted as a doubly excited bending vibration of the CO– ortho N 2 nuclear spin isomer. Hyperfine structure caused by two 14 N nuclei was partly resolved for the measured lines, and the quadrupole coupling constant, associated with the N 2 subunit, together with rotational and centrifugal distortion parameters were precisely determined for the new K = 0, ( j CO , j N2 ) = (2, 0) state. The high lying energy levels of this state provided a sensitive test for the recent ab initio potential energy surfaces.

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.

The ground state of He–HCO+ is investigated using a recently developed double resonance technique, consisting of a rotational transition followed by a vibrational transition into a dissociative state. In order to derive precise predictions for the rotational states, the high resolution infrared predissociation spectroscopy of the v1 C–H stretching mode is revisited. Eleven pure rotational transitions are measured via the double resonance method. A least squares fit of these transitions to a standard linear rotor Hamiltonian reveals that the semirigid rotor model cannot fully describe the loosely bound He–HCO+ complex. The novel double resonance technique is compared with other action spectroscopic schemes, and some potential future applications are presented.

New millimeter-wave transitions of the CO–N 2 van der Waals complex have been observed using the intracavity OROTRON jet spectrometer in the frequency range of 103–159 GHz. For the less abundant form, CO– para N 2 , a total of 37 rotational transitions were assigned to three K = 0–0, 0–1, 2–1 subbands connecting the ( j CO , j N2 ) = (1, 1) and ( j CO , j N2 ) = (0, 1) internal rotor states. The upper K = 0 and K = 2 “stacks” of rotational levels were probed for the first time here by millimeter-wave spectroscopy following a recent infrared study by Rezaei et al. (2013). The observation of new subbands fixes with higher precision not only these upper K = 0 and K = 2 but also lower K = 1( f ) levels, not linked with other stacks in earlier rotational studies. For the more abundant form, CO– ortho N 2 , five new P -branch rotational transitions of the K = 0–0 “CO bending” subband are reported, thus extending previous measurements. Nuclear quadrupole hyperfine structure due to the presence of two equivalent 14 N nuclei was partly resolved and analyzed to give additional information about the angular orientation of the N 2 molecule in the complex.

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 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.

The rotational spectrum of the CO-para-H2 van der Waals complex, produced using a molecular jet expansion, was observed with two different techniques: OROTRON intracavity millimeter-wave spectroscopy and pulsed Fourier transform microwave spectroscopy. Thirteen transitions in the frequency range from 80 to 130 GHz and two transitions in the 14 GHz region were measured and assigned, allowing for a precise determination of the corresponding energy level positions of CO-para-H2. The data obtained enable further radio astronomical searches for this molecular complex and provide a sensitive test of the currently best available intermolecular potential energy surface for the CO-H2 system.

A scientific session of the Physical Sciences Division of the Russian Academy of Sciences dedicated to the 40th anniversary of the Institute of Spectroscopy, RAS (ISAN) was held at ISAN on 8 October 2008. The following reports were presented at the session: (1) Balykin V I (ISAN) "Atom optics and nanotechnology"'; (2) Ryabtsev A N, Churilov S S (ISAN) "Spectroscopy of ionized atoms for astrophysics and nanotechnology"; (3) Lozovik Yu E (ISAN) "Strong correlations and new phases in a system of excitons and polaritons. A polariton laser"; (4) Vinogradov E A, Mavrin B N, Novikova N N, Yakovlev V A (ISAN) "Inverted optical phonons in ion-covalent crystals"; (5) Mal'shukov A G "Spin transport in semiconductor microstructures"; (6) Dumesh B S, Potapov A V, Surin L A (ISAN) "Spectroscopy of small helium clusters and 'nanoscopic' superfluidity: HeN – CO, N = 2 – 20..."; (7) Naumov A V, Vainer Yu G (ISAN) "Single molecules as spectral nanoprobes for the diagnostics of dynamic processes in solid media"; (8) Kompanets O N (ISAN), Yevdokimov Yu M (Engelhardt Institute of Molecular Biology, RAS) "Optical biosensors of genotoxicants based on DNA nanoconstructions and portable dichrometer." A brief presentation of these reports, with the exception of report 5, is given below. • Atom optics and nanotechnology, Physics-Uspekhi, 2009, Volume 52, Number 3, Pages 275–282 • Spectroscopy of ionized atoms for astrophysics and nanotechnology, Physics-Uspekhi, 2009, Volume 52, Number 3, Pages 282–286 • Strong correlations and new phases in a system of excitons and polaritons. A polariton laser, Physics-Uspekhi, 2009, Volume 52, Number 3, Pages 286–290 • Inverted optical phonons in ion-covalent crystals, Physics-Uspekhi, 2009, Volume 52, Number 3, Pages 290–293 • Spectroscopy of small helium clusters and 'nanoscopic' superfluidity: HeN – CO, N = 2 – 20..., Physics-Uspekhi, 2009, Volume 52, Number 3, Pages 294–298 • Single molecules as spectral nanoprobes for the diagnostics of dynamic processes in solid media, Physics-Uspekhi, 2009, Volume 52, Number 3, Pages 298–304 • Optical biosensors of genotoxicants based on DNA nanoconstructions and portable dichrometer., Physics-Uspekhi, 2009, Volume 52, Number 3, Pages 304–309

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.

Analysis of the rotational spectrum of the molecular dimer (CO)2 measured in the millimeter wave range has been performed and four new rotational states are revealed. Three of these states are characterized by almost free rotations of both monomers in the dimer. These states have approximately the same first term σ in the expansion of the rotational energy in powers of the rotational angular momentum J for various values of the momentum projections on the dimer axis (K=0, 1, 2) and various rotational constants B. The intrinsic rotational angular momenta of CO dimers, j1=j2=1, are determined from the σ value. In addition, a state with K=2 is found which corresponds to one of the known shape isomers of (CO)2. The values of the tunneling splitting for each of the new states are determined. The results indicate that previous data on the suppressed tunneling are determined by the asymmetry of internal rotations in the CO monomers rather than by the K value.

The millimeter wave spectrum of the isotopically substituted CO dimer, (13C16O)2, has been studied for the first time, confirming and extending a recent infrared study. Eighty-seven transitions in the 77-180?GHz region have been assigned and analyzed in terms of a model-independent term value scheme involving 57 rotational levels with J=0-8. The levels can be classified into 7 "stacks" which have symmetry classifications of either A-/B+ or A+/B- and K-values of either 0 or 1. For the normal isotope, symmetry and nuclear spin statistics cause alternate rotational levels to be missing, but for (13C16O)2 all levels are present with an intensity alternation of 1:3 between A and B symmetries. The four A-/B+ stacks have not previously been observed, and the lowest of them establishes the tunneling splitting of (13C16O)2 to be 3.769?cm-1, slightly larger than the (12C16O)2 value of 3.731?cm-1. A large amount of precise experimental data is now available for the CO dimer, which should lead to greater theoretical insight into its structure and tunneling dynamics.

The present state of research on the CO dimer is reviewed. In recent years, both infrared and millimeter-wave spectra have been measured and partially assigned by the use of combination differences. A microwave-millimeter wave double resonance experiment, reported here for the first time, provides independent confirmation of these assignments and the resulting (CO)2 energy level scheme. In the double resonance experiment, the OROTRON spectrometer functions as a supersensitive intra-cavity millimeter-wave detector. We update the continuing, but difficult, experimental efforts in recording the spectra, the quest for secure assignments, and the construction of a consistent and reliable energy level scheme. Although at present we have only limited knowledge of some aspects of the CO dimer, such as its geometrical structure, we have succeeded in characterizing unambiguously nine “stacks” of ground state energy levels with “microwave accuracy” (∼0.1 MHz). Every energy level within a given stack exhibits the same symmetry: either A− or A+. Only transitions between A+ and A− levels are allowed, and consequently ordinary pure rotational transitions within a stack are forbidden. Transitions between stacks can be thought of as tunneling transitions, and the separation of the lowest energy A+ and A− states corresponds to a value of 3.73 cm 1 for the effective “tunneling splitting” of the CO dimer. The stacks tend to fall into two groups, corresponding to “isomers” with effective inter-molecular separations of either 4.0 or 4.4 A. The larger inter-molecular separation of the true ground state (4.4 A) likely corresponds to a C-bonded configuration, while the low-lying (0.88 cm −1 ) excited state with the smaller separation (4.0 A) likely displays an O-bonded geometry.

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 review of recent results on the millimetre-wave spectroscopy of weakly bound van der Waals complexes, mostly those which contain H 2 and He, is presented. In our work, we compared the experimental spectra to the theoretical bound state results, thus providing a critical test of the quality of the M–H 2 and M–He potential energy surfaces (PESs) which are a key issue for reliable computations of the collisional excitation and de-excitation of molecules (M = CO, NH 3 , H 2 O) in the dense interstellar medium. The intermolecular interactions with He and H 2 play also an important role for high resolution spectroscopy of helium or para -hydrogen clusters doped by a probe molecule (CO, HCN). Such experiments are directed on the detection of superfluid response of molecular rotation in the He and p -H 2 clusters.

The interaction between ammonia and helium has attracted considerable interest over many years, partly because of the observation of interstellar ammonia. The rate coefficients of NH3 –He scattering are an important ingredient for numerical modeling of astrochemical environments. Another, though quite different application in which the NH3 –He interaction can play an important role is the doping of helium clusters with NH3 molecules to perform high-resolution spectroscopy. Such experiments are directed on the detection of non-classical response of molecular rotation in helium clusters addressing fundamental questions related to the microscopic nature of superfluidity. High-resolution spectroscopy on the NH3–He complex is an important tool for increasing our understanding of intermolecular forces between NH3 and He.

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.

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.

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 detailed description of a new ab initio interaction potential energy surfaces for the H2-CO complex computed on a six-dimensional grid (i.e., including the dependence on the H-H and C-O separations) is presented. The interaction energies were first calculated using the coupled-cluster method with single, double, and noniterative triple excitations and large basis sets, followed by an extrapolation procedure. Next, a contribution from iterative triple and noniterative quadruple excitations was added from calculations in smaller basis sets. The resulting interaction energies were then averaged over the ground-state and both ground- and first-excited-states vibrational wave functions of H2 and CO, respectively. The two resulting four-dimensional potential energy surfaces were fitted by analytic expressions. Theoretical infrared spectra calculated from these surfaces have already been shown [P. Jankowski, A. R. W. McKellar, and K. Szalewicz, Science 336, 1147 (2012)] to agree extremely well, to within a few hundredth of wavenumber, with the experimental spectra of the para and orthoH2-CO complex. In the latter case, this agreement enabled an assignment of the experimental spectrum, ten years after it had been measured. In the present paper, we provide details concerning the development of the surfaces and the process of spectral line assignment. Furthermore, we assign some transitions for paraH2-CO that have not been assigned earlier. A completely new element of the present work are experimental investigations of the orthoH2-CO complex using microwave spectroscopy. Vast parts of the measured spectrum have been interpreted by comparisons with the infrared experiments, including new low-temperature ones, and theoretical spectrum. Better understanding of the spectra of both para and orthoH2-CO complexes provides a solid foundation for a new search of the bound H2-CO complex in space.

Polycyclic Aromatic Hydrocarbons (PAHs) are widely accepted as the carriers of the Aromatic Infrared Bands (AIBs), but an unambiguous identification of any specific interstellar PAH is still missing. For polar PAHs, pure rotational transitions can be used as fingerprints for identification. Combining dedicated experiments, detailed simulations and observations, we explored the mm domain to search for specific rotational transitions of corannulene (C20H10). We performed high-resolution spectroscopic measurements and a simulation of the emission spectrum of UV-excited C20H10 in the environment of the Red Rectangle, calculating its synthetic rotational spectrum. Based on these results, we conducted a first observational campaign at the IRAM 30m telescope towards this source to search for several high-J rotational transitions of (C20H10). The laboratory detection of the J = 112 134 transition at 137.615 GHz. Comparing the noise level with the synthetic spectrum, we are able to estimate an upper limit to the fraction of carbon locked in corannulene of about 1.0x10(-5) relative to the total abundance of carbon in PAHs. The sensitivity achieved shows that radio spectroscopy can be a powerful tool to search for polar PAHs. We compare this upper limit with models for the PAH size distribution, emphasising that small PAHs are much less abundant than predicted. We show that this cannot be explained by destruction but is more likely related to the chemistry of their formation in the environment of the Red Rectangle., Comment: 8 pages, 7 figures, 2 tables, accepted for publication in MNRAS

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