MILLIMETER AND SUBMILLIMETER STUDIES OF O(1D) INSERTION REACTIONS TO FORM MOLECULES OF ASTROPHYSICAL INTEREST

While both the number of detected interstellar molecules and their chemical complexity continue to increase, understanding of the processes leading to their formation is lacking. Our research group combines laboratory spectroscopy, observational astronomy, and astrochemical modeling for an interdisciplinary examination of the chemistry of star and planet formation. This talk will focus on our laboratory studies of O($^1$D) insertion reactions with organic molecules to produce molecules of astrophysical interest. By employing these reactions in a supersonic expansion, we are able to produce interstellar organic reaction intermediates that are unstable under terrestrial conditions; we then probe the products using millimeter and submillimeter spectroscopy. We benchmarked this setup using the well-studied O($^1$D) + methane reaction to form methanol. After optimizing methanol production, we moved on to study the O($^1$D) + ethylene reaction to form vinyl alcohol (CH$_2$CHOH), and the O($^1$D) + methyl amine reaction to form aminomethanol (NH$_2$CH$_2$OH). Vinyl alcohol measurements have now been extended up to 450 GHz, and the associated spectral analysis is complete. A possible detection of aminomethanol has also been made, and continued spectral studies and analysis are underway. We will present the results from these experiments and discuss future applications of these molecular and spectroscopic techniques

A theoretical study of the conversion of gas phase methanediol to formaldehyde

Methanediol, or methylene glycol, is a product of the liquid phase reaction of water and formaldehyde and is a predicted interstellar grain surface species. Detection of this molecule in a hot core environment would advance the understanding of complex organic chemistry in the interstellar medium, but its laboratory spectroscopic characterization is a prerequisite for such observational searches. This theoretical study investigates the unimolecular decomposition of methanediol, specifically the thermodynamic and kinetic stability of the molecule under typical laboratory and interstellar conditions. Methanediol was found to be thermodynamically stable at temperatures of <100 K, which is the characteristic temperature range for interstellar grain mantles. The infinite-pressure RRKM unimolecular decomposition rate was found to be <10^(−18) s^(−1) at 300 K, indicating gas phase kinetic stability for typical laboratory and hot core temperatures. Therefore, both laboratory studies of and observational searches for this molecule should be feasible

A CSO Search for ll-C3_3H+^+: Detection in the Orion Bar PDR

The results of a Caltech Submillimeter Observatory (CSO) search for $l$-C$_3$H$^+$, first detected by Pety et al. (2012) in observations toward the Horsehead photodissociation region (PDR), are presented. A total of 39 sources were observed in the 1 mm window. Evidence of emission from $l$-C$_3$H$^+$ is found in only a single source - the Orion Bar PDR region, which shows a rotational temperature of 178(13) K and a column density of 7(2) x $10^{11}$ cm$^{-2}$. In the remaining sources, upper limits of ~10$^{11} - 10^{13}$ cm$^{-2}$ are found. These results are discussed in the context of guiding future observational searches for this species.Comment: 9 pages, 8 figures, 4 table

A search for ortho-benzyne (o-C6H4) in CRL 618

Polycyclic aromatic hydrocarbons (PAHs) have been proposed as potential carriers of the unidentified infrared bands (UIRs) and the diffuse interstellar bands (DIBs). PAHs are not likely to form by gas-phase or solid-state interstellar chemistry, but rather might be produced in the outflows of carbon-rich evolved stars. PAHs could form from acetylene addition to the phenyl radical (C6H5), which is closely chemically related to benzene (C6H6) and ortho-benzyne (o-C6H4). To date, circumstellar chemical models have been limited to only a partial treatment of benzene-related chemistry, and so the expected abundances of these species are unclear. A detection of benzene has been reported in the envelope of the proto-planetary nebula (PPN) CRL 618, but no other benzene-related species has been detected in this or any other source. The spectrum of o-C6H4 is significantly simpler and stronger than that of C6H5, and so we conducted deep Ku-, K- and Q-band searches for o-C6H4 with the Green Bank Telescope. No transitions were detected, but an upper limit on the column density of 8.4x10^13 cm^-2 has been determined. This limit can be used to constrain chemical models of PPNe, and this study illustrates the need for complete revision of these models to include the full set of benzene-related chemistry.Comment: 13 pages, 4 figures, to be published in The Astrophysical Journal Letter

Laboratory Astrophysics White Paper (based on the 2010 NASA Laboratory Astrophysics Workshop in Gatlinberg, Tennessee, 25-28 October 2010)

The purpose of the 2010 NASA Laboratory Astrophysics Workshop (LAW) was, as given in the Charter from NASA, "to provide a forum within which the scientific community can review the current state of knowledge in the field of Laboratory Astrophysics, assess the critical data needs of NASA's current and future Space Astrophysics missions, and identify the challenges and opportunities facing the field as we begin a new decade". LAW 2010 was the fourth in a roughly quadrennial series of such workshops sponsored by the Astrophysics Division of the NASA Science Mission Directorate. In this White Paper, we report the findings of the workshop

Complex Organic Molecules at High Spatial Resolution Toward Orion-KL I: Spatial Scales

Here we present high spatial resolution (<1 arcsecond) observations of molecular emission in Orion-KL conducted using the Combined Array for Research in Millimeter-Wave Astronomy (CARMA). This work was motivated by recent millimeter continuum imaging studies of this region conducted at a similarly high spatial resolution, which revealed that the bulk of the emission arises from numerous compact sources, rather than the larger-scale extended structures typically associated with the Orion Hot Core and Compact Ridge. Given that the spatial extent of molecular emission greatly affects the determination of molecular abundances, it is important to determine the true spatial scale for complex molecules in this region. Additionally, it has recently been suggested that the relative spatial distributions of complex molecules in a source might give insight into the chemical mechanisms that drive complex chemistry in star-forming regions. In order to begin to address these issues, this study seeks to determine the spatial distributions of ethyl cyanide [C2H5CN], dimethyl ether [(CH3)2O], methyl formate [HCOOCH3], formic acid [HCOOH], acetone [(CH3)2CO], SiO, methanol [CH3OH], and methyl cyanide [CH3CN] in Orion-KL at \lambda = 3 mm. We find that for all observed molecules, the molecular emission arises from multiple components of the cloud that include a range of spatial scales and physical conditions. Here we present the results of these observations and discuss the implications for studies of complex molecules in star-forming regions.Comment: Accepted for publication in the Astrophysical Journal Supplement; Part 1 of a 2 paper series; 37 page

CSO BROADBAND MOLECULAR LINE SURVEYS II: INTIAL CORRELATION ANALYSIS RESULTS FOR COMPLEX ORGANIC MOLECULES

Author Institution: Emory University, Department of Chemistry, Atlanta, Georgia 30322As was presented in the previous talk, we have conducted 25 broadband line surveys of interstellar sources in the $\lambda$=1.3 mm band using the Caltech Submillimeter Observatory. Using the results from the spectral analysis of these observations, the influence of physical environment on molecular complexity can be examined. Our broader research goal is to improve astrochemical models to the point where accurate predictions of complex molecular inventory can be made based on the physical and chemical environment of a given source. The CSO observations include a statistically-significant sample of sources, cover a range of physical environments, and target selected frequency windows containing transitions from a set of known complex organic molecules. We are now analyzing these line surveys to search for correlations between the relative abundances of organic molecules and the physical properties of the source (i.e. temperature, density, mass, etc.), as well as correlations between sets of molecules. Here we present the results from the initial quantitative analysis of these surveys, as well as chemical trends that have been determiend. The implications of these results for astrochemical models will also be discussed