Editorial Board: W. G. E. Caldwell, OC, FRSC (University of Western Ontario); K. G. Davey, OC, FRSC (York University); S. Gubins (Annual Reviews); B. K. Hall, FRSC (Dalhousie University); P. Jefferson (Agriculture & Agri-Food Canada); W. H. Lewis (Washington University); A. W. May, OC (Memorial University of Newfoundland); N. R. Morgenstern, CM, AOL, FRSC (University of Alberta); B. P. Dancik, Editor-in-Chief, NRC Research Press (University of Alberta)

Molecular symmetry and spectroscopy

Of the over 150 different molecular species detected in the interstellar and circumstellar media, approximately 50 contain 6 or more atoms. These molecules, labeled complex by astronomers if not by chemists, all contain the element carbon and so can be called organic. In the interstellar medium, complex molecules are detected in the denser sources only. Although, with one exception, complex molecules have only been detected in the gas phase, there is strong evidence that they can be formed in ice mantles on interstellar grains. The nature of the gaseous complex species depends dramatically on the source where they are found: in cold, dense regions they tend to be unsaturated (hydrogen-poor) and exotic, whereas in young stellar objects, they tend to be quite saturated (hydrogen-rich) and terrestrial in nature. Based on both their spectra and chemistry, complex molecules are excellent probes of the physical conditions and history of the sources where they reside. Because they are detected in young stellar objects, complex molecules are expected to be common ingredients for new planetary systems. In this review, we discuss both the observation and chemistry of complex molecules in assorted interstellar regions in the Milky Way.

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Complex Organic Interstellar Molecules

A set of spherical density basis functions for atoms sodium through argon have been obtained by least squares fitting of the corresponding electron density function for the ground state. These density functions, conveniently scaled, can be used in electron population analysis of molecules. To make this population analysis more flexible the density basis functions are split into two inner (K and L shell) parts and one outer (M shell) part. This technique gives populations which are relatively independent of the orbital bases used in spanning the molecular wavefunction. These density functions can be easily converted to scattering factors to be used in similar population analysis of accurate X-ray diffraction data.

Atoms in molecules

Designs for a broadband chirped pulse Fourier transform microwave (CP-FTMW) spectrometer are presented. The spectrometer is capable of measuring the 7-18 GHz region of a rotational spectrum in a single data acquisition. One design uses a 4.2 Gsampless arbitrary waveform generator (AWG) to produce a 1 mus duration chirped pulse with a linear frequency sweep of 1.375 GHz. This pulse is sent through a microwave circuit to multiply the bandwidth of the pulse by a factor of 8 and upconvert it to the 7.5-18.5 GHz range. The chirped pulse is amplified by a traveling wave tube amplifier and broadcast inside the spectrometer by using a double ridge standard gain horn antenna. The broadband molecular free induction decay (FID) is received by a second horn antenna, downconverted, and digitized by a 40 Gsampless (12 GHz hardware bandwidth) digital oscilloscope. The second design uses a simplified pulse generation and FID detection scheme, employing current state-of-the-art high-speed digital electronics. In this spectrometer, a chirped pulse with 12 GHz of bandwidth is directly generated by using a 20 Gsampless AWG and upconverted in a single step with an ultrabroadband mixer. The amplified molecular emission is directly detected by using a 50 Gsampless digital oscilloscope with 18 GHz bandwidth. In both designs, fast Fourier transform of the FID produces the frequency domain rotational spectrum in the 7-18 GHz range. The performance of the CP-FTMW spectrometer is compared to a Balle-Flygare-type cavity-FTMW spectrometer. The CP-FTMW spectrometer produces an equal sensitivity spectrum with a factor of 40 reduction in measurement time and a reduction in sample consumption by a factor of 20. The CP-FTMW spectrometer also displays good intensity accuracy for both sample number density and rotational transition moment. Strategies to reduce the CP-FTMW measurement time by another factor of 90 while simultaneously reducing the sample consumption by a factor of 30 are demonstrated.

A broadband Fourier transform microwave spectrometer based on chirped pulse excitation

We present a model of the longwave atmospheric spectrum that improves in many respects widely used older models such as the microwave propagation model (MPM), since it is based on broadband measurements and calculations. According to our data, the model is fully applicable from 0 to 2 THz while including lines up to 10 THz. Its primary goal is to simulate the millimeter/submillimeter region accessible from the ground (frequencies up to /spl sim/2 THz at most, with a few windows between 1 and 2 THz accessible only under exceptional conditions at very dry sites). Line-by-line calculations of the absorption are performed using a line database generated from the latest available spectroscopic constants for all relevant atmospheric species. The collisional line widths are obtained from published laboratory data. The excess of absorption in the longwave range that cannot be explained by the line spectrum is modeled by introducing two different continuum-like terms based on FTS measurements between 170 and 1100 GHz: collision-induced absorption of the dry atmosphere due to transient dipoles in symmetric molecules (N/sub 2/ and O/sub 2/) and continuum-like water vapor opacity. All H/sub 2/O lines up to 10 THz are included in order to correctly account for the entire H/sub 2/O far-wing opacity below 2 THz for a given line-shape. Hence, this contribution does not need to be part of a pseudocontinuum term below that frequency cutoff (still necessary, as shown in this paper) in contrast to other models used to date. Phase delays near H/sub 2/O and O/sub 2/ resonances are also important for ground-based astronomy since they affect interferometric phase. The frequency-dependent dispersive phase delay function is formally related to the absorption line shape via the Kramers-Kronig dispersion theory, and this relation has been used for modeling those delays. Precise calculations of phase delays are essential for the future Atacama large millimeter array (ALMA) project. A software package called atmospheric transmission at microwaves (ATM) has been developed to provide the radioastronomy and aeronomy communities with an updated tool to compute the atmospheric spectrum in clear-sky conditions for various scientific applications. We use this model to provide detailed simulations of atmospheric transmission and phase dispersion for several sites suitable for submillimeter astronomy.

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Atmospheric transmission at microwaves (ATM): an improved model for millimeter/submillimeter applications

Introduction Theoretical Aspects of Molecular Rotation Microwave Transitions - Line Intensities and Shapes Diatomic Molecules Linear Polyatomic Molecules Symmetric-Top Molecules Asymmetric-Top Molecules The Distortable Rotor Nuclear Hyperfine Structure in Molecular Rotational Spectra Effects of Applied Electric Fields Effects of Applied Magnetic Fields Internal Motions Derivation of Molecular Structures Quadrupole Couplings, Dipole Moments, and the Chemical Bond Irreducible Tensor Methods for Calculation of Complex Spectra Appendixes Author Index Subject Index.

Robert I. Cook

Papers

Microwave molecular spectra