Assignment and Power Series Analysis of the FIR Fourier Transform Spectrum of Cyanamide Using a Multimolecule Ritz Program

The “Ritz” program, originally written for the analysis of the Fourier transform spectra of the methanol isotopomers and presented in previous papers, has been extended in order to analyze the spectra of other molecules. This program evaluates the term values involved in the assigned transitions by the Rydberg–Ritz combination principle, and can tackle such perturbations as Fermi-type resonances or Coriolis interactions. As a first application of the extended version, we present an investigation of the Fourier transform spectrum of cyanamide between 25 and 980 cm⁻¹. More than 16 000 lines have been assigned. Our Ritz database now comprises a list of more than 19 000 assigned lines (including of the microwave and FIR lines available in the JPL database) and more than 3900 term values. All of the lines presented in this paper correspond to transitions within the ground and first excited inversion levels of the ground vibrational state of the small-amplitude modes.     

The QKa, Branches of Carbodiimide, HNCNH, between 1.8 and 3.3 THz

The ^rQ_Ka branches of carbodiimide, HNCNH, have been recorded with a tunable far-infrared spectrometer. The ^rQ_Ka branches with K_a { 2, 3, 4 }, which occur at approximately 1.8, 2.5, and 3.2 THz, respectively, were measured rotationally resolved. The torsional doublet splitting observed in the ^rQ₀ branch and several ^rR branches by Birk et al. (J. Mol. Spectrosc.136, 402-445 (1989)) was also observed in all the Q branches reported here. In addition, anomalous K_a-type doubling was detected within the ^rQ₂ branch for rotational quantum numbers J > 18. Molecular constants were obtained by fitting the line positions, including older data, with Watson′s Hamiltonian in S-reduction. The anomalous K_a-type doubling could be described as a centrifugal distortion interaction with ΔK_a = 4. The splitting is called anomalous because it inverts the K_a = 2 energy levels of an accidentally nearly prolate symmetric top molecule (Ray′s asymmetry parameter for HNCNH κ = −0.999995343(32)).     

On the waves and instability in self-gravitating magnetic molecular clouds with ambipolar diffusion Part 2: Cylindrical modal approach and nonlinear effects

The dynamics and evolution of molecular clouds, which are the main sites of active star formation in our Galaxy, are governed by the interaction of the self-gravity, magnetic fields, and ambipolar diffusion, in the form of waves and instability. In our earlier paper (Part 1), we carried out a detailed planar modal analysis. The present paper (Part 2) is an extension of Part 1 in order to include the three-dimensionality and the finite size of the cloud as well as the nonlinear effects. A cylindrical modal approach is developed to take into account the three-dimensionality and the finite size of the cloud as well as the special direction of the mean field B ₀. Dispersion relation and solutions of such cylindrical modes are obtained. It is shown that, in the most unstable direction (∥ B ₀), the growth rate is considerably reduced by the finite lateral size compared with the planar mode of the same wavelength. Nonlinear effects of the magnetic field and magnetic waves are discussed, with particular attention paid to their dependence on the coupling factor σ which is the ratio between the mean collision frequency of a neutral with ions and the gravitational response frequency. It is shown that fast magnetosonic waves are as important as Alfvén waves in the global support of the cloud. In order that the lower limit of the wavelengths in the moderately dissipative range of such waves is small compared with the cloud size, σ should be larger than 5. It is also shown that σ should be larger than 7.3 in order for the density growth of the neutral fluid in a free-fall time to be smaller than 30%. A typical value of σ ≈ 11 in molecular clouds is estimated. This corresponds to an ionization rate ζ = 10^?17 and a metal depletion δ = 0.1. For the clouds with such value of σ, both the density growth and the flux loss are smaller than 20% in a free-fall time. It is shown that a self-adjusting mechanism is able to slow down the global collapse at the early stage of cloud evolution in terms of the interaction between the global collapse and the then existing Alfvén and fast magnetosonic waves, which originate from the inhomogeneous velocity and density distributions in the cloud. Such interaction will not only strengthen these waves, but also create outwards decaying amplitudes of the field perturbation and therefore generate outward net magnetic forces to support the cloud against global collapse. The same mechanism also works for refreshing the outwards propagating Alfvén and fast magnetosonic waves caused by star-forming or core-forming activities, if the total energy supply rate due to these activities is lower than the total dissipation rate of these waves. In this way, a significant portion of the released gravitational energy during the global collapse is tapped and turned into the magnetic waves to slow down the global collapse itself. In terms of such a mechanism, the property that the dissipation rate of Alfvén and fast magnetosonic waves increases with the wave number leads to a simple explanation of the coexistence of the global quasi-stability and the local instability (formation of dense cores) in molecular clouds with cloud mass much larger than the Jeans mass.     

Inversion of the Ka = 0 and 1 rotational levels in the lowest excited vibrational state of HNCS

Fairly strong, regularly spaced absorption lines have been observed in the microwave spectrum of HNCS and assigned to b-type, K_a = 0 ← 1, Q-branch transitions arising from molecules in the lowest excited vibrational state. The Fortrat diagram of these lines has the appearance of a c-type Q branch, which is impossible in HNCS because of its symmetry. This anomalous b-type Q-branch spectrum is caused by strong a-type Coriolis interactions among the three low-lying bending modes; the K_a = 1 levels of the lowest excited vibrational state are perturbed and shifted lower in energy than the K_a = 0 levels for each J. This interpretation has been confirmed by the observation of P- and R-branch transitions associated with this Q branch. The band origin has been determined to be ?40 104.287 MHz (?1.3377 cm^?1). The inversion of the K_a = 0 and 1 energy levels is consistent with the interpretation of HNCS as a quasi-linear molecule.     

Ground state spectroscopic constants of H15NCS,HN13CS,and HNC34S,and the molecular structure of isothiocyanic acid

The rotational spectrum of isothiocyanic acid was measured for the isotopically enriched species H¹⁵NCS and HN¹³CS as well as HNC³⁴S in natural abundance. In the frequency range from 8 to 240 GHz the a-type R-branch transitions were measured for all three isotopic species. The ^qQ₁ transitions were identified in the microwave region for H¹⁵NCS and HN¹³CS. The rotational and centrifugal distortion constants were determined using Watson's Hamiltonian in the S reduction, extended empirically to higher order terms in the angular momentum. The molecular structure of isothiocyanic acid was reevaluated using a modified substitution method and the NCS chain was found to be bent: $\text{r(}\text{NH}\text{) = 0.993}\text{A}\text{?}$, $\text{r(}\text{NC}\text{) = 1.207}\text{A}\text{?}$, $\text{r(}\text{CS}\text{) = 1.5665}\text{A}\text{?}$, ∠HNC = 131.7°, and ∠NCS = 173.8°. The molecule has the trans conformation.     

Rotational Spectra of the Thiosulfeno Radical, HSS and DSS, between 0.3 and 0.9 THz

The rotational spectra of the HSS and DSS radicals were studied in selected regions between 331 and 883 GHz. The radicals were produced by discharging a gaseous mixture of hydrogen (or deuterium) and hydrogen sulfide in the cell. The observation of the b-type Q-branch and R-branch lines with K(a) = 2-1 and 3-2 for HSS and DSS, respectively, as well as the a-type R-branch lines allowed the improvement and the determination of the molecular constants among them (in MHz) We have reevaluated the harmonic force field of HSS and the ground state average and approximate equilibrium structural parameters. For the latter, we obtained r(HS) = 135.23 pm, r(SS) = 196.03 pm, and angle = 101.74 degrees. These results are compared with those from previous and own quantum chemical calculations as well as with results of related molecules. Copyright 2000 Academic Press.     

The torsion-rotation microwave spectrum of 12CH318OH and the structure of methanol

The microwave and millimeter wave spectrum of ¹²CH₃¹⁸OH has been observed in the frequency region 7.9–200 GHz. Both a- and b-type transitions have been assigned and measured. This spectrum was analyzed using the method of Lees and Baker, and rotational constants, torsional constants, centrifugal distortion constants, the barrier to internal rotation and moments of inertia have been evaluated. The barrier has been found to be 374.91 ± 0.18 cm^?1, in good agreement with that of ¹²CH₃¹⁶OH. The moments of inertia were combined with those of other isotopic species to give a full substitution structure. To assist searches for this molecule in interstellar space a table of predicted frequencies of astrophysically interesting transitions is presented.