Absolute Line Intensities for the nu6 Band of H2O2

The purpose of this work was to obtain reliable absolute intensities for the nu6 band of H2O2. It was undertaken because strong discrepancies exist between the different nu6 band intensities which are presently available in the literature (A. Perrin, A. Valentin, J.-M. Flaud, C. Camy-Peyret, L. Schriver, A. Schriver, and P. Arcas, J. Mol. Spectrosc. 1995. 171, 358), (R. May, J. Quant. Radiat. Transfer 1991. 45, 267), and (R. L. Sams, personal communication). The method which was chosen in the present work was to measure simultaneously the far-infrared absorptions and the nu6 absorptions of H2O2. Consequently, Fourier transform spectra of H2O2 were recorded at Giessen in a spectral range (370-1270 cm-1) which covers both the R branch of the torsion-rotation band and the P branch of the nu6 band which appear at low and high wavenumbers, respectively. From the low wavenumber data, the partial pressure of H2O2 present in the cell during the recording of the spectra was determined by calibrating the observed absorptions in the torsion-rotation band with intensities computed using the permanent H2O2 dipole moment measured by Stark effect (A. Perrin, J.-M. Flaud, C. Camy-Peyret, R. Schermaul, M. Winnewisser, J.-Y. Mandin, V. Dana, M. Badaoui, and J. Koput, J. Mol. Spectrosc. 1996. 176, 287-296) and [E. A. Cohen and H. M. Pickett, J. Mol. Spectrosc. 1981. 87, 582-583). In the high frequency range, this value of the partial pressure of H2O2 was used to measure absolute line intensities in the nu6 band. Finally, the line intensities in the nu6 band were fitted using the theoretical methods described in detail in our previous works. Using these new results on line intensities together with the line position parameters that we obtained previously, a new synthetic spectra of the nu6 band was generated, leading to a total band intensity of 0.185 x 10(-16) cm-1/(molecule.cm-2) at 296 K. It has to be pointed out that the new line intensities agree to within the experimental uncertainties with the individual line intensity measurements performed previously by May and by Sams. Copyright 1999 Academic Press.     

The Cologne Carbon Cluster experiment: ro-vibrational spectroscopy on C8 and other small carbon clusters

We report on our ongoing efforts in obtaining the IR-spectra of the linear carbon cluster molecules Cn with n=8-13. So far C8, C9, C10, and C13 have been recorded at Cologne. With the exception of C8 all assignments have been secured. For C8 a tentative assignment could be derived with the bandcenter of the sigmau antisymmetric stretching mode located at nu0=2067.9779 cm(-1) and a preliminary rotational constant in the vibrational ground state of B"=0.02068 cm(-1). The measured signal to noise ratio of the ro-vibrational band is fairly weak and thus the lower J ro-vibrational transitions can not be assigned with certainty. As a consequence the band center remains uncertain by 4 J or 0.17 cm(-1). For a more reliable assignment the sensitivity of the system has to be increased by at least one order of magnitude. The envisaged sensitivity increase of our experiment will be discussed along with the intention to perform terahertz observations of the low energetic bending ro-vibrational spectra. These sub-mm wave measurements will be carried out simultaneously with the IR measurements.     

Vibrationally excited states of HC5N: millimeter-wave spectroscopy and coupled cluster calculations

The rotational spectrum of HC₅N has been investigated in the millimeter-wave region, from 60 to 290 GHz, for 15 vibrationally excited states which lie approximately between 500 and 860 cm⁻¹, namely (v₆ v₇ v₈ v₉ v₁₀ v₁₁) = (000005), (000006), (000007), (000008), (000020), (000030), (001000), (010000), (100000), (000021), (000101), (001001), (010001), (000110), and (001010). Gas-phase copyrolysis of pyridine and phosphorus trichloride or, alternatively, a dc discharge in a gaseous mixture of vinyl cyanide and acetylene were used to produce the semi-stable HC₅N molecule. A large number of vibrational and rovibrational interactions has been taken into account to fit properly the measured transition frequencies of the states investigated. The most important perturbations are caused by the high-order Coriolis resonances observed between the (v₈, v₁₀) and (v₈ − 1, v₁₀ + 2) states, and between the (v₇, v₁₀, v₁₁) and (v₇ − 1, v₁₀ + 3, v₁₁ − 1) states, and by the cubic anharmonic interactions which mix the (v₆, v₈, v₁₁) states with the (v₆ − 1, v₈ + 1, v₁₁ + 1) states, and the (v₆, v₁₀) states with the (v₆ − 1, v₁₀ + 2) states. The analysis of the spectra was facilitated by CCSD(T) calculations with the cc-pVQZ basis, which provided accurate predictions of a large variety of spectroscopic constants like harmonic vibrational wavenumbers, vibration–rotation coupling constants, l-type doubling constants, and normal-coordinate cubic force constants. Excellent agreement between experiment and theory was generally observed, even when the experimental data were strongly perturbed by resonance effects.     

On the waves and instability in self-gravitating magnetic molecular clouds with ambipolar diffusion Part 1: Planar modal approach

It is well established that molecular clouds are the main sites of active star formation in our Galaxy. The interaction of the three major physical agents in molecular clouds, i.e. the self-gravity, magnetic fields, and ambipolar diffusion, in the form of waves and instability, governs the dynamics and evolution of molecular clouds. The present work is a new effort on this subject. This work consists of two parts. In Part 1, we complete the planar modal analysis by removing the restrictions on the direction of the velocity perturbation which were used in previous studies. Thus, the wave number vector k is allowed to take any direction with respect to the mean field B₀. The exact general dispersion relation is found to be a seventh-order equation and can be reduced to a quartic equation as the first approximation about the small parameter x_ρ = ρ_{i, 0}/ρ_n,0, the density ratio between ions and neutrals. The growth rate contour maps in the k plane are obtained for various values of the basic dimensionless parameters Λ and σ, where Λ = V_A,n/C_n is the ratio between the Alfvén speed and the sound speed in the neutrals, and the “coupling factor” σ = v_i/ω_g,n is the ratio between the average collision frequency of a neutral with ions and the self-gravitation response frequency. It is shown that, in all directions, magnetic field only reduces the growth rate but does not change the critical wave length for instability. The reduction of the growth rate depends on not only Λ, the dimensionless measure of the field strength, but also the direction of k as well as the coupling factor σ. The frequencies and the dissipation rates of the Alfvén waves and the fast and slow self-gravitating magnetosonic waves are calculated for all directions of k. The solutions of these waves are also given. Although the planar modal approach is important in understanding the basic mechanism of magnetic waves and instability, it does not take into account the three-dimensionality and the finite size of the cloud and is therefore only suitable to the local analysis. Thus, in order to discuss the global properties, we will develop a cylindrical modal approach in Part 2. There, we will also discuss certain nonlinear effects and show their importance in leading to a self-adjusting mechanism which slows down the global collapse at the early stage of cloud evolution and refreshes the outward propagating Alfvén and fast magnetosonic waves caused by star-forming or core-forming activities. In this way, a significant portion of the released gravitational energy during the global collapse is turned into the magnetic waves to support the cloud against the global collapse itself.     

The FT-IR Spectrum of HCNO: The ν1, ν2, 2ν3, and ν2 + ν3 Band Systems

The infrared spectrum of HC¹⁵NO an isotopically substituted species of fulminic acid, has been measured in the range 1900-3600 cm⁻¹ at a resolution of 0.003 cm⁻¹ with a Bruker IFS 120 HR interferometer. More than 100 subbands have been assigned. Power series coefficients for these transitions are given. A Coriolis resonance between the levels 01002 (l = 0e) and 01010 (l = 1e) allows normally "forbidden" transitions to occur, some of which were observed and assigned. We correlate transition intensities and energies of the resonance system. Variations in the manifold of nν₅ states with excitation of other modes are compared.     

Rotational spectra of the 13C and 15N isotopic species of cyanoacetylene

Ground vibrational state rotational transitions have been measured in the frequency region 8 to 220 GHz for the following four isotopic species of cyanoacetylene: H¹³CCCN, HC¹³CCN, HCC¹³CN, and HCCC¹⁵N. The improved rotational constants were used for accurate frequency predictions for any transition not measured in this frequency range. Cyanoacetylene was produced efficiently by a radiofrequency discharge in a mixture of HCCH and HCN; this technique provides a convenient method for specific isotopic enrichment of this molecule.     

ACTIVATION ENERGY OF DESORPTION OF DIBENZOFURAN ON ACTIVATED CARBONS

1. INTRODUCTION With the development of municipalization in China, more and more cities are challenged by the problem of how to dispose of the dramatically increased municipal waste. Generally, most of municipal solid waste is landfilled or dumped openly in the suburbs. It causes not only land waste, but also serious environment pollution. In order to solve efficiently the environment pollution caused by municipal solid waste, incineration technique was introduced in some big cities such…     

Conformations of highly hindered aryl ethers: IX. Dipole moment evidence for an intramolecular donor-acceptor complex

In a search for evidence that a π cloud proximal halogen interaction is of importance to the mode of action of the thyroid hormones, the dipole moments of the 1'-naphthyl (I), (4.29 D), 4'-carboxymethylphenyl (II), (2.90 D), 2'-bromo4'-carboxymethylphenyl (III), (3.56 D), and methyl (IV), (3.24 D) ethers of 2,4dinitro-6-bromophenol were determined in benzene at 25 °C. The moments of (I), (II) and (III) are approximated best by those calculated for the twisted conformation in which the bromine closely approaches the face of the other ring. That of the naphthyl ether (I) can, however, be explained only by inclusion of an intramolecular electron donor-acceptor charge-transfer moment of 1.6 D directed from the π cloud of the naphthyl ring to the proximal nitro group of the other ring, or of 2.8 D to the proximal bromine of that ring. In the preferred conformation of the methyl ether (IV), the methoxy group is coplanar with the ring while the 2-nitro group is twisted 90° from coplanarity to accomodate it. A mesomeric moment of 2.3 D is estimated from this for the 2,4-dinitro-6-bromophenoxy moiety and is used in calculating the expected moments of the other ethers.