Intercomparison between ozone-broadening parameters retrieved from millimetre-wave measurements by using different techniques

For atmospheric purposes, the N₂- and O₂-, or Air-broadenings of selected transitions of ozone have been investigated in the 195-300 K temperature range. More precisely, the following 13 transitions in the 280-345 GHz frequency range have been studied: the 2_2,0 ← 2_1,1 (279.5 GHz), 24_2,22 ← 24_1,23 (286.2 GHz), 3_2,2 ← 3_1,3 (286.3 GHz), 5_2,4 ← 5_1,5 (293.2 GHz), 13_4,10 ← 14_3,11 (300.7 GHz), 14_0,14 ← 13_1,13 (301.8 GHz), 7_2,6 ← 7_1,7 (303.2 GHz), 26_2,24 ← 26_1,25 (315.9 GHz), 5_3,3 ← 6_2,4 (317.2 GHz), 20_1,19 ← 20_0,20 (320.0 GHz), 26_6,20 ← 27_5,23 (343.2 GHz), 26_2,24 ← 25_3,23 (343.2 GHz), and 4_3,1 ← 5_2,4 (343.5 GHz) lines. Systematic errors are known to be the principal error source and recent intercomparisons of line-broadening coefficients showed differences up to 20%, thus a large effort in minimizing systematic error sources has been taken and cross check measurements with different techniques have been carried out. The conclusion of the intercomparison performed indicates an excellent agreement of the results and that an uncertainty less than 3%, which also takes into account the systematic errors, can be claimed for the line-broadening parameters.     

The equilibrium C-H bond length

The equilibrium C-H bond length has been determined up to now for about 40 polyatomic molecules. These data are used to demonstrate the existence of quantitative correlations betweenr _e(C-H), isolated C-H bond stretching frequency and average distancer _g. It is also shown that ab initio calculations are often reliable to calculate the absolute value ofr _e(C-H), if an empirical correction is made. Some other correlations are also discussed. Finally, accurater _e(C-H) values are predicted for simple molecules.     

Rovibrational and Rotational Spectroscopy of Levels of Propyne around 1000 cm(-1)

Four vibrational levels in the energy region around 1000 cm(-1) were studied. These were the v(5)=1 and v(8)=1 fundamental levels, both components of the v(9)=v(10)=1 combination level (l(9)=l(10)=+/-1 and l(9)=-l(10)=+/-1), and both components of the v(10)=3 overtone level (l(10)=+/-1 and +/-3). New FTIR spectra with a synchrotron radiation source were recorded in the region of the "superhot" v(10)=3<--2 bands, which made possible the first assignment of levels of the v(10)=3(+/-1) sublevel. More than 330 new rotational transitions in the combination and overtone levels were measured by millimeter-wave spectroscopy betwen 50 and 360 GHz. The new data were analyzed simultaneously together with the previously assigned rovibrational data for the fundamental and combination levels and rotational data for the fundamental levels using a global model with all anharmonic, Coriolis, l-type, and alpha-resonances. Significant improvement of data reproduction and very good consistency with the Hamiltonian parameters of the lower vibrational levels v(9)=1 and v(10)=1, 2 were achieved. A strong dependence of the A(v) constant on the l(10) quantum number is found for propyne: this is shown to be characteristic of skeleton C-C identical withC or C-C identical withN bending modes in H(3)CCCH, H(3)CCN, and their fully deuterated species. Copyright 2001 Academic Press.     

Microwave Spectrum of 1-Cyano-3-fluoro-but-1-ene

The rotational spectrum of the 1-cyano-3-fluoro-but-1-ene has been recorded with a pulsed-nozzle microwave Fourier transform spectrometer over the range 6-20 GHz. The frequencies were fitted to the Hamiltonian of Watson (A-reduction, I(r) representation). The resulting rotational constants are A = 7493.404(1) MHz, B = 1211.9831(2) MHz, and C = 1096.0908(1) MHz. By comparing the experimental rotational constants with those obtained by ab initio calculations, we found without ambiguity that the stable conformation for the molecule is the one with the fluorine atom lying in the C&bond;CCN plane (CF-eclipsed conformer). Copyright 2000 Academic Press.     

Relaxation and Lineshape of the 500.4-GHz Line of Ozone Perturbed by N(2) and O(2)

N(2)- and O(2)-broadened linewidths of the J = 34(2,32) <-- 34(1,33) transition of ozone located at 500.4 GHz have been measured at three temperatures in the 247-295 K range by using a video-type spectrometer. Besides the Voigt profile commonly used as theoretical model for millimeter-wave investigations, different other theoretical lineshapes, the speed-dependent Voigt profile, the Galatry profile, and the speed-dependent Galatry profile, have been considered to analyze the experimental spectra, to retrieve the pressure-broadening parameters, and to give an account of the pointed out line-narrowing effect. The results for O(3) perturbed by N(2) and O(2) are finally compared to calculations based on the complex semiclassical theory of Robert and Bonamy, and with previous reported values involving the same kind of transitions. Finally, it is shown that observed line narrowings result nearly exclusively from the dependence of relaxation on molecular speeds. Copyright 2000 Academic Press.     

New far infrared measurements of the rotational spectrum of cyanoacetylene HC3N

Several rotational lines of cyanoacetylene in the ground state and the first excited state v7=1 have been measured between 580 and 1100 GHz with a new FIR laser sidebands spectrometer. A global analysis which takes into account the previous measurements on this molecule is performed.     

Internal rotation and chlorine nuclear quadrupole coupling of o-chlorotoluene studied by microwave spectroscopy and ab initio calculations

The microwave spectrum of o-chlorotoluene has been reinvestigated using molecular beam Fourier transform microwave (MB-FTMW) spectrometers in the frequency range of 4–23 GHz. Due to the high resolution of this molecular beam technique the analysis yielded improved rotational constants, centrifugal distortion constants, and, for the first time, the complete chlorine nuclear quadrupole coupling tensor. From the torsional fine structure the barrier to internal rotation of the methyl group was found to be 5.5798(52) kJ mol⁻¹. Experimental results and ab initio calculations are compared.     

A sensitivity study on spectroscopic parameter accuracies for a mm/sub-mm limb sounder instrument

The purpose of this paper is to perform a detailed error analysis for a mm/sub-mm limb sounding instrument with respect to spectroscopic parameters. This is done in order to give some insight into the most crucial spectroscopic parameters and to work out a list of recommendations for measurements that would yield the largest possible benefit for an accurate retrieval. The investigations cover a variety of spectroscopic line parameters, such as line intensity, line position, air and self broadening parameters and their temperature exponents, and pressure shift. The retrieval process is performed with the optimal estimation method (OEM). The OEM allows one to perform an assessment of the total statistical error, as well as of the model parameter error, such as the error coming from spectroscopic parameters. The instrument parameters assumed are those of the MASTER instrument studied by the European Space Agency, one of the candidate instruments for a future atmospheric chemistry mission. However, the same principle and method of analysis can be applied to any other millimeter/sub-millimeter limb sounding instrument, for instance the Japanese instrument JEM/SMILES, the Swedish instrument Odin, and the Earth Observing System Microwave Limb Sounder. We find that an uncertainty in the intensity of the strong lines give an error of similar magnitude on the retrieved species to which the lines belong. Uncertainties in the line position have overall a small impact on the retrieval, indicating that the line positions are known with sufficient accuracy. The air broadening parameters and their temperature exponents of a few strong lines dominate the error budget. On the other hand, the self broadening parameters and the pressure shifts are found to have a rather small impact on the retrieval.     

The Millimeter-Wave Spectrum of 2,3-Dihydrofuran

The millimeter-wave spectrum of 2,3-dihydrofuran in the ground and five ring-puckering excited states has been measured in the frequency range 100–250 GHz. The ground and first ring-puckering excited states have been fitted to a two-state Hamiltonian including Coriolis coupling interaction. The determined energy difference of 18.684(7) cm⁻¹between these states and theaandbtype coupling parameters are consistent with the ring-puckering potential function and the previously observed dependence of the centrifugal distortion constants Δ_JK, Δ_K, and δ_K. A small ring-puckering dependence of the quartic centrifugal distortion constants Δ_Jand δ_Jhas been also observed. This dependence is well accounted for in terms of the ring-puckering potential function and the vibrational dependence of the rotational constants.