Valerio Lattanzi

LABORATORY AND TENTATIVE INTERSTELLAR DETECTION OF TRANS-METHYL FORMATE USING THE PUBLICLY AVAILABLE GREEN BANK TELESCOPE PRIMOS SURVEY

The rotational spectrum of the higher-energy trans conformational isomer of methyl formate has been assigned for the first time using several pulsed-jet Fourier transform microwave spectrometers in the 6-60 GHz frequency range. This species has also been sought toward the Sagittarius B2(N) molecular cloud using the publicly available PRIMOS survey from the Green Bank Telescope. We detect seven absorption features in the survey that coincide with laboratory transitions of trans-methyl formate, from which we derive a column density of 3.1 (+2.6, -1.2) \times 10^13 cm-2 and a rotational temperature of 7.6 \pm 1.5 K. This excitation temperature is significantly lower than that of the more stable cis conformer in the same source but is consistent with that of other complex molecular species recently detected in Sgr B2(N). The difference in the rotational temperatures of the two conformers suggests that they have different spatial distributions in this source. As the abundance of trans-methyl formate is far higher than would be expected if the cis and trans conformers are in thermodynamic equilibrium, processes that could preferentially form trans-methyl formate in this region are discussed. We also discuss measurements that could be performed to make this detection more certain. This manuscript demonstrates how publicly available broadband radio astronomical surveys of chemically rich molecular clouds can be used in conjunction with laboratory rotational spectroscopy to search for new molecules in the interstellar medium.

On the molecular structure of HOOO.

The molecular structure of trans, planar hydridotrioxygen (HOOO) has been examined by means of isotopic spectroscopy using Fourier transform microwave as well as microwave-millimeter-wave double resonance techniques, and high-level coupled cluster quantum-chemical calculations. Although this weakly bound molecule is readily observed in an electrical discharge of H(2)O and O(2) heavily diluted in an inert buffer gas, we find that HOOO can be produced with somewhat higher abundance using H(2) and O(2) as precursor gases. Using equal mixtures of normal and (18)O(2), it has been possible to detect three new isotopic species, H(18)OOO, HO(18)O(18)O, and H(18)O(18)O(18)O. Detection of these species and not others provides compelling evidence that the dominant route to HOOO formation in our discharge is via the reaction OH + O(2) → HOOO. By combining derived rotational constants with those for normal HOOO and DOOO, it has been possible to determine a fully experimental (r(0)) structure for this radical, in which all of the structural parameters (the three bond lengths and two angles) have been varied. This best-fit structure possesses a longer central O-O bond (1.684 Å), in agreement with earlier work, a markedly shorter O-H bond distance (0.913 Å), and a more acute [angle]HOO angle (92.4°) when compared to equilibrium (r(e)) structures obtained from quantum-chemical calculations. To better understand the origin of these discrepancies, vibrational corrections have been obtained from coupled-cluster calculations. An empirical equilibrium (r(e) (emp)) structure, derived from the experimental rotational constants and theoretical vibrational corrections, gives only somewhat better agreement with the calculated equilibrium structure and large residual inertial defects, suggesting that still higher order vibrational corrections (i.e., γ terms) are needed to properly describe large-amplitude motion in HOOO. Owing to the high abundance of this oxygen-chain radical in our discharge expansion, a very wide spectral survey for other oxygen-bearing species has been undertaken between 6 and 25 GHz. Only about 50% of the observed lines have been assigned to known hydrogen-oxygen molecules or complexes, suggesting that a rich, unexplored oxygen chemistry awaits detection and characterization. Somewhat surprisingly, we find no evidence in our expansion for rotational transitions of cis HOOO or from low-lying vibrationally excited states of trans HOOO under conditions which optimize its ground state lines.

Spatial Distributions and Interstellar Reaction Processes

Methyl formate presents a challenge for the conventional chemical mechanisms assumed to guide interstellar organic chemistry. Previous studies of potential formation pathways for methyl formate in interstellar clouds ruled out gas-phase chemistry as a major production route, and more recent chemical kinetics models indicate that it may form efficiently from radical-radical chemistry on ice surfaces. Yet, recent chemical imaging studies of methyl formate and molecules potentially related to its formation suggest that it may form through previously unexplored gas-phase chemistry. Motivated by these findings, two new gas-phase ion-molecule formation routes are proposed and characterized using electronic structure theory with conformational specificity. The proposed reactions, acid-catalyzed Fisher esterification and methyl cation transfer, both produce the less stable trans-conformational isomer of protonated methyl formate in relatively high abundance under the kinetically controlled conditions relevant to interstellar chemistry. Gas-phase neutral methyl formate can be produced from its protonated counterpart through either a dissociative electron recombination reaction or a proton transfer reaction to a molecule with larger proton affinity. Retention (or partial retention) of the conformation in these neutralization reactions would yield trans-methyl formate in an abundance that exceeds predictions under thermodynamic equilibrium at typical interstellar temperatures of ≤100 K. For this reason, this conformer may prove to be an excellent probe of gas-phase chemistry in interstellar clouds. Motivated by new theoretical predictions, the rotational spectrum of trans-methyl formate has been measured for the first time in the laboratory, and seven lines have now been detected in the interstellar medium using the publicly available PRIMOS survey from the NRAO Green Bank Telescope.

The pure rotational spectrum of HPS (X̃1A′): Chemical bonding in second-row elements

The pure rotational spectrum of HPS, as well as its (34)S and D isotopologues, has been recorded at microwave, millimeter, and submillimeter wavelengths, the first observation of this molecule in the gas phase. The data were obtained using a combination of millimeter direct absorption, Fourier transform microwave (FTMW), and microwave-microwave double-resonance techniques, which cover the total frequency range from 15 to 419 GHz. Quantum chemical calculations at the B3LYP and CCSD(T) levels were also performed to aid in spectral identification. HPS was created in the direct absorption experiment from a mixture of elemental phosphorus, H(2)S, and Ar carrier gas; DPS was produced by adding D(2). In the FTMW study, these species were generated in a pulsed discharge nozzle from PH(3) and H(2)S or D(2)S, diluted in neon. The spectra recorded for HPS and its isotopologues exhibit clear asymmetric top patterns indicating bent structures; phosphorus hyperfine splittings were also observed in HPS, but not DPS. Analysis of the data yielded rotation, centrifugal distortion, and phosphorus nuclear spin-rotation parameters for the individual species. The r(m) ((1)) structure for HPS, calculated from the rotational constants, is r(H-P) = 1.438(1) Å, r(P-S) = 1.9320(1) Å, and θ(H-P-S) = 101.85(9)°. Empirically correcting for zero-point vibrational effects yields the geometry r(e)(H-P) = 1.4321(2) Å, r(e)(P-S) = 1.9287(1) Å, and θ(e)(H-P-S) = 101.78(1)°, in close agreement with the r(m) ((1)) structure. A small inertial defect was found for HPS indicating a relatively rigid molecule. Based on these data, the bonding in this species is best represented as H-P=S, similar to the first-row analog HNO, as well as HNS and HPO. Therefore, substitution of phosphorus and sulfur for nitrogen and oxygen does not result in a dramatic structural change.

Laboratory detection of protonated SO2 in two isomeric forms

By means of Fabry-Pérot Fourier transform microwave spectroscopy, the rotational spectrum of protonated sulfur dioxide in two distinct isomeric forms, a cis- and a trans-geometry, is reported. The search for both isomers was based on theoretical structures obtained at the CCSD(T)/cc-pwCVQZ level of theory corrected for zero-point vibrational effects. At a similarly high level of theory, the cis-isomer is calculated to be the global minimum on the potential energy surface, but the trans-isomer is predicted to lie only a few kcal/mol higher in energy. A total of seven lines, including a- and b-type transitions, has been observed for both isomers, and precise rotational constants have been derived. Because sulfur dioxide, SO(2), is a widespread and very abundant astronomical species, and because it possesses a large proton affinity, HOSO(+) is an excellent candidate for radioastronomical detection.

The Rotational Spectrum of the NCO– Anion

The rotational spectrum of the negative molecular ion NCO– has been observed both in a supersonic molecular beam and in a low-pressure glow discharge. The identification is ironclad because of the previous infrared detection of NCO–, the presence of well-resolved nitrogen quadrupole hyperfine structure, and the observation of nine harmonically related transitions in the millimeter band. The spectroscopic constants B and D are three orders of magnitude more accurate than those derived from the earlier IR measurements, and the theoretical eQq is in good agreement with that measured. The entire rotational spectrum can now be calculated well into the THz region to 1 km s–1 in equivalent radial velocity or better. NCO– is an excellent candidate for radio astronomical detection because of its high stability, polarity, and favorable partition function. The fairly high concentration of NCO– in our laboratory source implies that other molecular anions containing the NCO group may be detectable in the radio band.

Accurate sub-millimetre rest frequencies for HOCO+ and DOCO+ ions

Context. HOCO + is a polar molecule that represents a useful proxy for its parent molecule CO 2 , which is not directly observable in the cold interstellar medium. This cation has been detected towards several lines of sight, including massive star forming regions, protostars, and cold cores. Despite the obvious astrochemical relevance, protonated CO 2 and its deuterated variant, DOCO + , still lack an accurate spectroscopic characterisation. Aims. The aim of this work is to extend the study of the ground-state pure rotational spectra of HOCO + and DOCO + well into the sub-millimetre region. Methods. Ground-state transitions have been recorded in the laboratory using a frequency-modulation absorption spectrometer equipped with a free-space glow-discharge cell. The ions were produced in a low-density, magnetically confined plasma generated in a suitable gas mixture. The ground-state spectra of HOCO + and DOCO + have been investigated in the 213–967 GHz frequency range; 94 new rotational transitions have been detected. Additionally, 46 line positions taken from the literature have been accurately remeasured. Results. The newly measured lines have significantly enlarged the available data sets for HOCO + and DOCO + , thus enabling the determination of highly accurate rotational and centrifugal distortion parameters. Our analysis shows that all HOCO + lines with K a ≥ 3 are perturbed by a ro-vibrational interaction that couples the ground state with the v 5 = 1 vibrationally excited state. This resonance has been explicitly treated in the analysis in order to obtain molecular constants with clear physical meaning. Conclusions. The improved sets of spectroscopic parameters provide enhanced lists of very accurate sub-millimetre rest frequencies of HOCO + and DOCO + for astrophysical applications. These new data challenge a recent tentative identification of DOCO + towards a pre-stellar core.

LABORATORY MEASUREMENTS AND TENTATIVE ASTRONOMICAL IDENTIFICATION OF H2NCO

The rotational spectrum of H_2NCO^+, the ground-state isomer of protonated HNCO, has been measured in a molecular beam in the centimeter band with a Fourier transform microwave spectrometer and in a low-pressure laboratory discharge in absorption in the millimeter band. Spectroscopic constants, including the nitrogen-14 hyperfine coupling constant, derived from 30 a-type transitions between 20 and 367 GHz with J ≤ 18 and K_a ≤ 3 allow the principal rotational transitions to be calculated to 1 km s^(–1) or better in equivalent radial velocity well into the far IR. Two low-lying rotational transitions of H_2NCO^+ in the centimeter band (0_(0,0)-1_(0,1) and 1_(1,0)-2_(1,1)) were tentatively identified in absorption in the PRIMOS spectral line survey of Sgr B2(N) with the Green Bank Telescope. The lines of H_2NCO^+ arise in a region of the Sgr B2(N) halo whose density is low (n < 1 × 10^4 cm^(–3)). The derived column density of (6-14) × 10^(11) cm^(–2) implies that the fractional abundance is ~10^(–12). Owing to the ubiquity of HNCO in galactic molecular clouds, H_2NCO^+ is a good candidate for detection in sources spanning a wide range of physical conditions.

Detection of nitrogen-protonated nitrous oxide (HNNO+) by rotational spectroscopy.

The rotational spectrum of nitrogen-protonated nitrous oxide (HNNO(+)), an isomer whose existence was first inferred from kinetic studies more than 30 years ago, has now been detected by Fourier transform microwave spectroscopy, guided by new high-level coupled-cluster calculations of its molecular structure. From high-resolution measurements of the hyperfine splitting in its fundamental rotational transition, the rotational constant (B + C)/2 and the quadrupole tensor element χaa(N) for both nitrogen atoms have been precisely determined. The derived constants agree well with quantum-chemical calculations here and others in the literature. The χaa(N) values for the two isomers of protonated nitrous oxide are qualitatively consistent with the valence bond description of H-N═N(+)═O for the electronic structure of the nitrogen-protonated form and N≡N(+)-O-H for the oxygen-protonated form. HNNO(+) is found to be 2-4 times less abundant than NNOH(+) under a range of experimental conditions, as might be expected because this metastable isomer is known to be only ∼6 kcal mol(-1) less stable than ground-state NNOH(+) from kinetic measurements by Ferguson and co-workers.

The rotational spectrum of protonated sulfur dioxide, HOSO +

Aims. We report on the millimeter-wave rotational spectrum of protonated sulfur dioxide, HOSO + . Methods. Ten rotational transitions between 186 and 347 GHz have been measured to high accuracy in a negative glow discharge. Results. The present measurements improve the accuracy of the previously reported centimeter-wave spectrum by two orders of magnitude, allowing a frequency calculation of the principal transitions to about 4 km s −1 in equivalent radial velocity near 650 GHz, or one linewidth in hot cores and corinos. Conclusions. Owing to the high abundance of sulfur-bearing molecules in many galactic molecular sources, the HOSO + ion is an excellent candidate for detection, especially in hot cores and corinos in which SO2 and several positive ions are prominent.