THz measurements of propane

Propane is present in many planetary atmospheres, as confirmed by vibrational spectroscopy in the infrared wavelengths. As the simplest alkane with a permanent dipole moment, propane has a rotational spectrum. The relatively light atom framework causes the strongest rotational transitions to appear in the submillimeter wavelength range. This fact, as well as the small dipole moment, have prevented the molecule from being observed in the interstellar medium. Telescopes with high sensitivity at high altitude such as the Atacama Large Millimeter Array or above the Earth’s atmosphere like the Herschel Space Observatory are likely to be sensitive enough for detection of this species in the interstellar medium, planetary nebulae, hot cores and/or planetary atmospheres. We present the rotational spectra of propane in its ground and first two excited vibrational states, measured through 1.6 THz. The ground state submillimeter spectrum is approximated well by semi-rigid rotor. The submillimeter data has been combined with high resolution centimeter wavelength data to enable analysis of the equivalent dual-hindered rotor torsional substates using a simplified version of a symmetric two-top Hamiltonian. The same model has been applied to the torsionally excited states that experience more large-amplitude motion and require additional tunnelling parameters.     

Microwave spectrum,dipole moment,and structure of 3-aminopropanol

The microwave spectra of 3-aminopropanol and three of its deuterium substituted isotopic species have been investigated in the 26.5 to 40 GHz frequency region. The rotational spectrum of only one conformer has been assigned in which presumably a hydrogen bond of the OH---N type exists. The rotational spectra of a number of excited vibrational states have been observed and assignments made for some of these excited states. The average intensity ratio for the rotational transitions between the ground and excited vibrational states indicates that the first excited state is about 120 cm^?1 above the ground state.and the next higher state is roughly 200 cm^?1 above the ground vibrational state. The dipole moment was determined from the Stark effect measurements to be 3.13 ± 0.04 D with its principal axes components as |μ_a| = 2.88 ± 0.03 D, |μ_b| = 1.23 ± 0.04 D and |μ_c| = 0.06 ± 0.01 D. The possibility of another conformer where the hydrogen bond could be of NH---O type was explored, but the spectra of such a conformer could not be identified.     

The millimeter and submillimeter spectrum of CN in its first four vibrational states

The rotational absorption frequencies of 65 new lines in the millimeter and submillimeter region of the spectrum have been measured for the CN radical in its ground electronic state. These measurements were made in a low pressure glow discharge of methane and nitrogen and include 25 lines from the v = 2 and v = 3 vibrational states, in addition to 40 lines from v = 0 and v = 1. The Dunham constants, as well as the spin-rotation and hyperfine constants of these four vibrational states, were calculated by means of a global nonlinear least squares fit of these data.     

The microwave spectrum of isotopically substituted hypochlorous acid: Determination of the molecular structure

Microwave spectra have been measured for four isotopically substituted species of hypochlorous acid (D¹⁶O³⁵Cl, D¹⁶O³⁷Cl, H¹⁸O³⁵Cl, H¹⁸O³⁷Cl). Both a- and b-type transitions have been analyzed for rotational, centrifugal distortion, and Cl nuclear quadrupole coupling constants. The distortion constants, together with vibrational wavenumbers, have been used to evaluate a valence harmonic force field. Effective, substitution, ground state average, and estimated equilibrium structures are presented.     

The Millimeter-Wave Spectrum of Chlorine Nitrate (ClONO2): The 2ν9 and ν7 Vibrational States

Chlorine nitrate is a molecule of interest in atmospheric studies because of its role as a reservoir species, removing both chlorine and nitrogen species from catalytic cycles of ozone destruction. The ground and ν₉ vibrational states have been previously studied in the millimeter and submillimeter spectral regions. We have now recorded and analyzed the next states that are lowest in energy, the coupled 2ν₉/ν₇ dyad, from 128 through 355 GHz using a fast scan submillimeter spectroscopic technique system.     

Role of weak transitions in multiphoton excitation of molecules by IR laser radiation

Simultaneous excitation of a considerable part of molecules from many rotational levels of the ground state to higher vibrational states by IR laser radiation can be explained by considering weak transitions in a rotational band structure as it is shown at the example of SF₆ molecule. Very accurate compensation of anharmonicity in relatively wide spectral interval at comparatively low intensity of laser radiation can be explained on this basis. The considered scheme can be applied to the molecules of various symmetry with arbitrary anharmonicity.     

Submillimeter wave spectrum and molecular constants of N2O

The submillimeter wave spectrum of the N₂O molecule has been investigated within the 375–565 GHz frequency range with a sensitivity better than 10^?8 cm^?1. The measured frequencies include 161 lines with intensities γ ? 10^?6 cm^?1 belonging to 22 spectroscopically different species of the molecule (specifically, the ground and some excited vibrational states of the five most abundant isotopic species of the molecule in natural abundance) with a statisticall and systematic error of the order of magnitude 10^?8. Rotational and two centrifugal stretching constants could be determined for each spectroscopic species. For each isotopic species observed, we have made a general analysis of the spectrum in different vibrational states bearing in mind resonance effects. The total number of the rotational and rovibrational constants obtained exceeds 40.     

New measurements of the microwave spectrum of formamide

New measurements of the microwave spectrum of formamide have been obtained in the frequency range from 49 to 340 GHz using the microwave spectrometer at the Institute of Radio Astronomy of NASU, Kharkov, Ukraine. An analysis of the rotational spectra of the ground, v₁₂, v₉, v₁₁ and 2v₁₂ excited vibrational states of the main isotopic species as well as of the ground states of the ¹³C, ¹⁵N and ¹⁸O substituted species has been carried out using SPFIT/SPCAT programs. The analysis of a strong Coriolis interaction coupling between v₉, v₁₁ and 2v₁₂ vibrational states of formamide has been also fulfilled as well as the analysis of the quadrupole hyperfine structure of the observed transitions. For the first time the quadrupole coupling parameters for the excited vibrational states and for the ¹⁸O substituted species of formamide were determined.     

The absorption spectrum of 12C2H2 between 12800 and 18500cm−1 II. Rotational analysis

The rotational structure of the vibrational bands of ¹²C₂H₂ is investigated in three spectral energy regions not previously systematically explored at high resolution, 12800–13500 cm^?1, 14000–15200 cm^?1 and 16500–18360 cm^?1, on the basis of new spectral data recorded by intracavity laser absorption spectroscopy. The rotational analysis of 17 new absorption bands arising from the ground state is reported (11 Σ_u ⁺ ? Σ_g ⁺ bands and 6Π_u ? Σ_g ⁺ bands). Four bands in the range studied show strong perturbations affecting both the line positions and intensities. Their detailed analysis is performed in order to determine the nature of the coupling schemes, the vibrational species and the rotational constants of the perturber states. Altogether, the vibration-rotation parameters of 21 newly observed vibrational states are derived.     

High-Lying Rotational Levels of Water: An Analysis of the Energy Levels of the Five First Vibrational States

As a continuation of the work carried out on the ground and (010) vibrational states of water (R. Lanquetin, L. H. Coudert, and C. Camy-Peyret, 1999, J. Mol. Spectrosc. 195, 54-57), rotational energy levels for these two states are revisited here and new accurate rotational energy levels are considered for the three next vibrational states, that is, the (020), (100), and (001) states. Experimental rotational energies, along with their uncertainties, are retrieved through analyses of already published data sets and of discharge and flame emission spectra. The maximum value of J for the obtained levels is 25 for the ground state, 21 for the (010) state, and 20 for the three next states. Based on the bending-rotation Hamiltonian approach (L. H. Coudert, 1997, J. Mol. Spectrosc. 181, 246-273), a new theoretical approach is proposed to calculate rotational energies in the five interacting vibrational states under consideration and is used to carry out an analysis of the experimental energies. Comparisons with other existing energy level data sets are also presented. Copyright 2001 Academic Press.     

Millimeter and submillimeter wave rotational spectrum of pyridine in the ground and excited vibrational states

The pure rotational spectra of the ground and five excited vibrational states of pyridine were measured, assigned and fit in the 75-110 and 260-370 GHz frequency bands. An improved set of spectroscopic constants was obtained for the ground state, and all the rotational and quartic centrifugal distortion constants were obtained for the excited vibrational states.     

The millimeter and submillimeter rotational spectrum of 1,3-dihydroxyacetone

Recent detection of the 2C sugar glycolaldehyde in the Sgr B2(N-LMH) hot core source as well as the presence of several sugars and other polyhydroxylated species in the Murchison meteorite have led to interest in observational searches for higher order sugars in the interstellar medium. 1,3-Dihydroxyacetone, the simplest 3C sugar, is one of the species detected in Murchison and is of considerable importance for observational searches as the next step in complexity for interstellar sugars. However, little spectroscopic information is available for this molecule. We present here the Doppler-limited rotational spectrum of 1,3-dihyroxyacetone to 450 GHz. Assignments include the ground state up to J=104 and four additional vibrational states. Standard rotational and quartic centrifugal distortion constants have been determined for each of these states.     

Resonance enhanced coherent anti-stokes raman scattering and laser induced fluorescence applied to CH radicals: a comparative study

Resonance enhanced CARS and LIF have been applied to the CH radicals in a microwave excited Ar/H/CH plasma ( Pa, kW). Both techniques yield similar nonthermal rotational population distributions of CH(X) in its vibrational ground state (), which can be described by two rotational temperatures, K being in the order of the gas temperature for rotational states with , and a considerably higher for the higher rotational states. This result is in good agreement with previous resonance CARS and LIF measurements in similar plasmas. With resonance CARS additional measurements on CH in the state could be performed yielding a vibrational temperature of 2440 K, the total CH density was about m. The detection limits of both techniques are determined, in our case about CH radicals per quantum state in the detection volume, and their advantages and disadvantages are discussed. Received: 29 April 1996 / Accepted: 19 June 1996     

Room temperature chirped-pulse Fourier transform microwave spectroscopy of anisole

The room-temperature rotational spectrum of anisole from 8.7 to 18.3 GHz was collected with a waveguide-based chirped-pulse Fourier transform microwave spectrometer whose operating principles are described. Three spectra were assigned, corresponding to the vibrational ground state and the first and second excited states of the lowest frequency torsional mode. Results for the ground state and first excited state are in agreement with prior millimeter wave studies of this molecule. Microwave–microwave double resonance measurements also confirm these assignments.     

Optical diagnostics for temperature measurement in a DC arcjet reactor used for diamond deposition

2 a-state in this plume. LIF measurements of CH are complicated by the presence of C₃ and we discuss strategies to deal with this interference. The gas temperature describing the rotational distributions obtained for NO, C₂ and CH agree within experimental error. Optical emission measurements indicate that the rotational and vibrational distributions of the excited A-state of CH and a-state of C₂ are characterized by vibrational and rotational populations which are at least 1000 K above the ground state distributions. The excited states are collisionally quenched before their population distributions equilibrate with the gas temperature. We also determine relative populations of the ground and excited states along the axis of the plume between the arcjet nozzle and the substrate and relative populations for a cross section of the jet, midway between the nozzle orifice and the substrate. The measured relative ground and excited state populations for both CH and C₂ show different trends along the plume axis, indicating that the ground and excited states of these molecules are products of different chemical mechanisms; such mechanisms are discussed. Received: 16 July 1996/Revised version: 24 September 1996     

Laser spectroscopy of desorbing molecules

In this article the application of tunable dye lasers to desorption phenomena is illuminated. These lasers provide radiation continuously tunable from 105 nm in the vacuum ultraviolet to about 10 m in the mid-IR. By employing either laser induced fluorescence (LIF) or resonance enhanced multiphoton ionization (REMPI) spectroscopy almost all diatomic and many polyatomic molecules can be probed with the sensitivity required to detect desorbing molecules under UHV conditions. The spectral resolution of the lasers is sufficiently high that rotational state selectivity is achieved. Recent developments permit in addition the velocity distributions of molecules to be determined with internal quantum state resolution. Therefore very detailed information about the molecular dynamics has been obtained. In most experiments so far reactive recombinations off surfaces have been investigated. In this paper special emphasis will be given to the recombination of hydrogen on copper and palladium surfaces. For these systems very detailed data about the internal state populations at various surface temperatures have been obtained. The rotational cooling previously observed in molecular beam scattering has also been established for desorption. Strong vibrational excitation has been observed, which in the case of desorption from copper may be associated with the recombination dynamics, whereas for desorption of D₂ from Pd(100) a molecular precursor state might be responsible. By measuring the velocity distribution in each quantum state, the complete energetics of the desorbing molecules has been determined. Some first experiments on laser induced desorption with state selective detection of the desorbing molecules will also be discussed. Finally, making use of the polarization analysis of the signal, alignment effects in the desorption can be observed, permitting observation of molecular dynamics with a magnifying glass.Heisenberg fellow of the Deutsche Forschungsgemeinschaft     

Pure Rotational Spectra of SO: Rare Isotopomers in the 80-GHz to 1.1-THz Region

Pure rotational spectra of rare isotopomers of sulfur monoxide, SO, have been recorded with the Cologne Terahertz Spectrometer, Germany, and the millimeter- and submillimeter-wave spectrometer at Nobeyama, Japan. In total, 176 new transitions have been measured in theX³Σ⁻electronic ground state, including the first laboratory detection of the rare isotopomer³⁶SO. New lines are also reported for³³SO and S¹⁷O in their vibrational ground states, and for³³SO and S¹⁸O in the first excited vibrational state. A simultaneous fit of 451 transitions has led to an improved set of isotopically invariant parameters for rotation and fine structure. Hyperfine structure constants for³³SO and S¹⁷O have been obtained also from the global fit, including first values for the magnetic nuclear spin–rotation interaction. These are compared to other molecules. The isotopically invariant parameters allow precise frequency predictions for the submillimeter-wave region far beyond 1 THz for all SO isotopomers, of importance to astrophysical applica- tions.     

The microwave spectrum of sodium tetrahydroborate NaBH4 in excited vibrational states: Coriolis interaction between the Na-BH4 stretching and the BH4 rocking vibrations

Two sets of vibrational satellites have been observed in the rotational spectrum of sodium tetrahydroborate NaBH₄, and have been assigned to the non-degenerate, Na—BH₄ stretching and the degenerate BH₄ rocking (or internal rotation) states. The observation was extended from the J = 11 ← 10 up to J = 20 ← 19 transitions. The vibrational satellites showed anomalous K structure; higher-K lines of the non-degenerate state appeared at higher frequencies, in reverse to those of the ground state, whereas the spectra in the degenerate state exhibited a K pattern similar to but somewhat more widely spread than that of the ground state. These anomalies are ascribed to the Coriolis interaction between the two excited vibrational states. The spectra observed were analysed using a C_3v symmetric-top rotational Hamiltonian, which took into account the Coriolis interaction explicitly. The A rotational constants, the energy difference δE between the two interacting vibrational states, and the first- and second-order Coriolis interaction constants have been derived.     

The microwave spectrum,structure, and dipole moment of propiolyl fluoride

The microwave spectrum of propiolyl fluoride has been observed in the frequency region 12.5–40 GHz. Rotational transitions have been assigned for the ground and two excited vibrational states of the normal isotopic species and for the ground vibrational state of the deuterated species. In each case, values for the rotational constants and centrifugal distortion constants have been obtained. The molecule has been shown to be planar and structural calculations suggest no anomalies in any of the internuclear parameters. Stark effect measurements have yielded a value of 2.98 ± 0.02 Debyes for the dipole moment.     

Terahertz absorption spectrum of D2O vapor

The absorption spectrum of D₂O vapor from 0.2 to 2.0 THz (6.7-67 cm⁻¹) which is associated with rotational modes was measured at one atmosphere using terahertz time-domain spectroscopy (THz-TDS). The linewidth and collisional dephasing times were measured for 26 pure rotational transitions in the ground vibrational state (0 0 0). The temperature dependence of the linewidth (Δν) behaves as Δν ∼ T^−3/4 and the linewidth decrease with increasing temperature is attributed to the 1/r⁶ force of interaction between colliding D₂O molecules.