No abstract

Reactive open-shell species, such as radicals and biradicals, are key intermediates in the formation of (poly)cyclic hydrocarbon species in a variety of interstellar environments, ranging from cold molecular clouds to the outflows of carbon-rich stars. In this work, we identify the products of the o-benzyne + methyl radical reaction isomer-selectively by photoion mass-selected threshold photoelectron spectroscopy. We assign the benzyl (C 7 H • 7 ) radical as the sole intermediate of the association reaction. Subsequent hydrogen atom loss from benzyl yields the five-membered ring species fulvenallene (FA), 1-ethynylcyclopentadiene (1ECP), and 2-ethynylcyclopentadiene (2ECP) which have recently been detected in the cold molecular cloud TMC-1. We report a comprehensive C 7 H 7 potential energy surface (PES) of the title reaction and show that the products form via direct barrierless addition followed by ring-contraction and hydrogen elimination. A statistical model predicts 89% 1ECP, 8% FA, and 3% 2ECP branching ratios at 0 K. Astrochemical simulations of TMC-1 incorporating this reaction result in the excellent reproduction of the abundance of a five-membered ring species, 1ECP, and provide strong evidence for the in situ "bottomup" formation of small cyclic species in cold cores. Last, we put the results in context of the recent detection of fulvenallene in TMC-1.

Ortho-benzyne is a potentially important precursor for polycyclic aromatic hydrocarbon formation, but much is still unknown about its chemistry. In this work, we report on a combined experimental and theoretical...

Methanol is ubiquitous in star-forming regions, and has recently been detected in a protoplanetary disk. Astrochemical models have shown that methanol photolysis contributes to complex organic chemistry in interstellar ices. While some methanol photolysis branching ratios have been measured, infrared condensed-phase measurements rely on assumptions about the chemistry, and mass spectrometric measurements cannot distinguish structural isomers. To address these challenges, we are using pure rotational spectroscopy to quantitatively probe the methanol photolysis products. We use a VUV laser to dissociate methanol in the throat of a supersonic expansion, and probe the products downstream after cooling is complete. We then use a rotational diagram analysis to determine the relative density of each product relative to methanol. We have detected the methoxy, hydroxymethyl, and formaldehyde photolysis products. We present here the experimental setup and the initial results and discuss these results in the context of interstellar chemistry.

Microwave-millimeter/submillimeter wave double-resonance spectroscopy has been developed with the use of technology typically employed in chirped pulse Fourier transform microwave spectroscopy and fast-sweep direct absorption (sub)millimeter-wave spectroscopy. This technique offers the high sensitivity provided by millimeter/submillimeter fast-sweep techniques with the rapid data acquisition offered by chirped pulse Fourier transform microwave spectrometers. Rather than detecting the movement of population as is observed in a traditional double-resonance experiment, instead we detected the splitting of spectral lines arising from the AC Stark effect. This new technique will prove invaluable when assigning complicated rotational spectra of complex molecules. The experimental design is presented along with the results from the double-resonance spectra of methanol as a proof-of-concept for this technique.