Spectroscopy among the stars

The space between the stars is not void, but filled with interstellar matter, mainly composed of dust and gas, which gather in large interstellar clouds. In our Galaxy these interstellar clouds are distributed along a thin, but extended layer which basically traces out the spiral distribution of matter: the stars, the gas, and the dust component. Up to the present time more than 100 different molecules have been identified in interstellar molecular clouds. The majority of the interstellar molecules constitute carbon containing organic substances. During the past years, overwhelming evidence has been gathered, mainly through spectroscopic observations, that interstellar molecular clouds provide the birthplaces for stars. In fact detailed high spectral and spatial resolution spectroscopic measurements reveal physical and chemical processes of the intricate star formation process.     

The millimeter wave rotational spectrum of N-cyanomethanimine,CH2NCN

The rotational spectrum of the short-lived species N-cyanomethanimine, CH₂NCN, has been measured in the frequency range 100–250 GHz. The observed transitions allow the determination of the rotational and centrifugal distortion constants and the nitrogen quadrupole coupling constants for both nitrogen nuclei. The N-cyanomethanimine spectrum was measured directly in the products of the pyrolysis of trimethylenetetrazole. The rotational constants obtained are A = 63 372.995(11) MHz, B = 5 449.347 90(28) MHz, and C = 5 009.559 86(29) MHz; the quadrupole coupling constants are χ_aa = 2.057(39) MHz and χ_bb ? χ_cc = ?7.205(21) MHz for the imine nitrogen, and χ_aa = ?3.264(33) MHz and χ_bb ? χ_cc = ?1.630(18) MHz for the cyano-group nitrogen. The accurate constants obtained allow the calculation of the line position and hyperfine structure of any rotational transition appropriate for a radioastronomical search.     

The rotational a-type sepctra of 15N-labeled diazirine,H2CN2

The rotational a-type spectra of isotopically enriched diazirine isotopomers, H₂¹²C¹⁴N¹⁵N and H₂¹²C¹⁵N₂, have been recorded in the region between 8 and 300 GHZ; the latter isotopomer has been observed for the first time. Using Watson's A-reduced Hamiltonian, the rotational constants and the quartic and some sextic centrifugal distortion constants have been determined for the ground vibrational states.     

Vibration-rotation interaction in HCNO caused by accidental resonances and enhanced by the quasilinearity of the molecule

The recent assignment of the vibrational spectrum of the quasilinear molecule HCNO revealed several near coincidences between vibrational energy levels involving the two bending modes, ν₄ (skeletal bending mode) and ν₅ (HCN-bending mode), and the lowest-lying stretching mode, ν₃ (NO stretching mode). By considering the correlation between the energy levels of a linear and a bent molecular model of HCNO, it is seen that resonance interactions which would be of third or higher order in a linear molecule Hamiltonian would be of first or second order in the Hamiltonian of a bent molecule, and thus might be significant in the quasilinear molecule HCNO. In this way we were able to identify the type of observed interaction occurring between three pairs of nearly coincident levels, (00010, 00002), (00020, 00012), and (00100, 00004). Anomalous centrifugal distortion effects had been observed and reported earlier for the pure rotational transitions arising from molecules in the 00010, 00020, and 00002 levels. Rotational transitions arising from molecules in the 00004 and 00100 vibrational states of HCNO and the 00100 state of DCNO are reported here for the first time. For two pairs of levels, (00010, 00002) and (00100, 00004), we could determine the magnitude of the coefficients of the interaction matrix elements from an analysis of the centrifugal distortion effects.     

HCNO as a semirigid bender

The semirigid bender Hamiltonian [Bunker and Landsberg, J. Mol. Spectrosc., 67, 374–385 (1977)] is used to fit the rotation-vibration energy level separations in the fulminic acid (HCNO) molecule. The allowance made in the model for the variation of the CH and CN bond lengths with the HCN bending angle proves to be very important, and as well as achieving a good fit we are able to make a detailed investigation of the shape of the HCN bending potential function.From the results we conclude that the equilibrium structure of HCNO is linear but that excitation of the ν₁ or ν₂ stretching vibrations gives rise to an effective HCN bending potential function having its minimum at a nonlinear configuration. Even in the ground state the zeropoint vibrational contributions from ν₁ and ν₂ to the effective HCN bending potential give a small barrier (11.5 cm^?1) to linearity, and we determine that the zero-point HCN bending vibrational amplitude is ±34°.     

Isotope effects in the CO dimer: millimeter wave spectrum and rovibrational calculations of (12C18O)2

The millimeter wave spectrum of the isotopically substituted CO dimer, (12C18O)2, was studied with the Orotron jet spectrometer, confirming and extending a previous infrared study [A. R. W. McKellar, J. Mol. Spectrosc. 226, 190 (2004)]. A very dilute gas mixture of CO in Ne was used, which resulted in small consumption of 12C18O sample gas and produced cold and simple spectra. Using the technique of combination differences together with the data from the infrared work, six transitions in the 84-127 GHz region have been assigned. They belong to two branches, which connect four low levels of A+ symmetry to three previously unknown levels of A- symmetry. The discovery of the lowest state of A- symmetry, which corresponds to the projection K=0 of the total angular momentum J onto the intermolecular axis, identifies the geared bending mode of the 12C18O dimer at 3.607 cm(-1). Accompanying rovibrational calculations using a recently developed hybrid potential from ab initio coupled cluster [CCSD(T)] and symmetry-adapted perturbation theory calculations [G. W. M. Vissers et al., J. Chem. Phys. 122, 054306 (2005)] gave very good agreement with experiment. The isotopic dependence of the A+/A- energy splitting, the intermolecular separation R, and the energy difference of two ground state isomers, which change significantly when 18O or 13C are substituted into the normal (12C16O)2 isotopolog [L. A. Surin et al., J. Mol. Spectrosc. 223, 132 (2004)], was explained by these calculations. It turns out that the change in anisotropy of the intermolecular potential with respect to the shifted monomer centers of mass is particularly significant.     

Effect of radiative cooling on collapsing charged grains

The effect of the radiative cooling of electrons on the gravitational collapse of cold dust grains with fluctuating electric charge is investigated. We find that the radiative cooling as well as the charge fluctuations, both, enhance the growth rate of the Jeans instability. However, the Jeans length, which is zero for cold grains and nonradiative plasma, becomes finite in the presence of radiative cooling of electrons and is further enhanced due to charge fluctuations of grains resulting in an increased threshold of the spatial scale for the Jeans instability.     

Diode laser spectrum of the ν6 band of CH3I using a novel étalon as a calibration scale

The ΔK = Δl = +1 transitions of the ν₆ band of the CH₃I molecule were measured by a tunable diode laser spectrometer. A newly designed Fabry-Perot étalon with a free spectral range of 0.00945 cm^?1 was used to calibrate the line position very precisely. The present data were analyzed together with the previously reported transition wavenumbers, and precise molecular constants have been obtained.     

Automatic Structure Determination of Organic Molecules： Principle and Implementation of the LSD Program

The LSD (Logic for Structure Determination) program gener-ates organic molecular structures from 1D and 2D NMR data without resorting to chemical shift databases. Its use in the res-olution of natural product structure determination problems has been already reported in the literature. This paper describes how data and structures are internally represented and pro-cessed by LSD to build solution structures.