Brent J. Harris

HERSCHEL OBSERVATIONS OF EXTRAORDINARY SOURCES: ANALYSIS OF THE FULL HERSCHEL/HIFI MOLECULAR LINE SURVEY OF SAGITTARIUS B2(N) ∗

A sensitive broadband molecular line survey of the Sagittarius B2(N) star-forming region has been obtained with the Heterodyne Instrument for the Far-Infrared (HIFI) instrument on the Herschel Space Observatory, offering the first high spectral resolution look at this well-studied source in a wavelength region largely inaccessible from the ground (625–157 μm). From the roughly 8000 spectral features in the survey, a total of 72 isotopologues arising from 44 different molecules have been identified, ranging from light hydrides to complex organics, and arising from a variety of environments from cold and diffuse to hot and dense gas. We present a local thermodynamic equilibrium (LTE) model to the spectral signatures of each molecule, constraining the source sizes for hot core species with complementary Submillimeter Array interferometric observations and assuming that molecules with related functional group composition are cospatial. For each molecule, a single model is given to fit all of the emission and absorption features of that species across the entire 480–1910 GHz spectral range, accounting for multiple temperature and velocity components when needed to describe the spectrum. As with other HIFI surveys toward massive star-forming regions, methanol is found to contribute more integrated line intensity to the spectrum than any other species. We discuss the molecular abundances derived for the hot core where the LTE approximation is generally found to describe the spectrum well, in comparison to abundances derived for the same molecules in the Orion KL region from a similar HIFI survey. Notably, we find significantly higher abundances of amine- and amide-bearing molecules (CH_3NH_2, CH_2NH, and NH_2CHO) toward Sgr B2(N) than Orion KL and lower abundances of some complex oxygen-bearing molecules (CH_3OCHO in particular). In addition to information on the chemical composition of the hot core, the strong far-infrared dust continuum allows a number of molecules to be detected in absorption in the Sgr B2(N) envelope for the first time at high spectral resolution, and we discuss the possible physical origin of the kinematic components observed in absorption. Additionally, from the detection of new HOCO^+ transitions in absorption compared to published HCO^+ isotopic observations, we discuss constraints on the gas-phase CO_2 abundance and compare this to observations of the ice composition in the Galactic center region, and to CO_2 abundance estimates toward other high-mass star-forming regions. The reduced HIFI spectral scan and LTE model are made available to the public as a resource for future investigations of star-forming regions in the submillimeter and far-infrared.

Segmented chirped-pulse Fourier transform submillimeter spectroscopy for broadband gas analysis.

Chirped-pulse Fourier transform spectroscopy has recently been extended to millimeter wave spectroscopy as a technique for the characterization of room-temperature gas samples. Here we present a variation of this technique that significantly reduces the technical requirements on high-speed digital electronics and the data throughput, with no reduction in the broadband spectral coverage and no increase in the time required to reach a given sensitivity level. This method takes advantage of the frequency agility of arbitrary waveform generators by utilizing a series of low-bandwidth chirped excitation pulses paired in time with a series of offset single frequency local oscillators, which are used to detect the molecular free induction decay signals in a heterodyne receiver. A demonstration of this technique is presented in which a 67 GHz bandwidth spectrum of methanol (spanning from 792 to 859 GHz) is acquired in 58 μs.

Pure rotational spectrometers for trace-level VOC detection and chemical sensing

Pure rotational spectroscopy in the centimeter, millimeter, and THz regions of the electromagnetic spectrum is a powerful technique for the characterization of polar molecules in the gas phase. Although this technology has a long history in the research sector for structural characterization, recent advances in digital electronics have only recently made commercial instruments competitive with established chemical analysis techniques. BrightSpec is introducing a platform of pure rotational spectrometers in response to critical unmet needs in chemical analysis. These instruments aim to deliver the operational simplicity of Fourier transform infrared spectrometers in conjunction with the chemical analysis capabilities of mass spectrometers. In particular, the BrightSpec ONE instrument a broadband gas mixture analyzer with full capabilities for chemical analysis. This instrument implements Fourier transform millimeter-wave emission spectroscopy, wherein a brief excitation pulse is applied to the sample, followed by the measurement of the coherent free induction decay responses of all molecular transitions within the excitation bandwidth. After sample injection and characterization, the spectrometer returns a list of all known species detected in the sample, along with their concentrations in the mixture. No prior knowledge about the sample composition is required. The instrument can then perform double-resonance measurements (analogous to 2-D COSY NMR), direct mass determination through analysis of the time profile of the molecular signal, and automated isotopic identification as part of a suite of tools that can return the structural identity of the unknowns in the sample.

Fourier transform molecular rotational resonance spectroscopy for reprogrammable chemical sensing

Molecular rotational resonance (MRR) spectroscopy gives spectral signatures with high chemical selectivity. At room temperature, the peak intensity of the MRR spectrum occurs in the 100 GHz – 1 THz frequency range for volatile species with mass ≤ 100 amu. Advances in high-power sub-mm-wave light sources has made it possible to implement time-domain Fourier transform (FT) spectroscopy techniques that are similar to FT nuclear magnetic resonance (FT-NMR) measurements. In these measurements, the gas sample is excited by a short (200 ns) excitation pulse that creates a macroscopic sample polarization. The electric field of the subsequent transient molecular emission is detected using a heterodyne receiver and a high-speed digitizer. FT-MRR spectroscopy offers speed and sensitivity improvements over absorption spectroscopy. For chemical analysis, FT-MRR spectrometers combine the benefits of broad chemical coverage typical of gas chromatography – mass spectrometry (GC-MS) instruments and the direct measurement capabilities of infrared gas sensors all in a reprogrammable platform. Pulse sequence measurements can be implemented for advanced spectroscopic analysis. Trace level quantitation of volatile species at ppbv concentration can be performed on the time scale of a minute. In cases where the sample is a complex mixture, a double-resonance pulse sequence can be used to achieve chemical selectivity even in cases where spectral overlap occurs. These measurement capabilities are illustrated using the application of FT-MRR spectroscopy to residual solvent analysis of pharmaceutical products.