Cosmic-ray-mediated Formation of Benzene on the Surface of Saturn's Moon Titan

The aromatic benzene molecule (C_6H_6)—a central building block of polycyclic aromatic hydrocarbon molecules—is of crucial importance for the understanding of the organic chemistry of Saturn's largest moon, Titan. Here, we show via laboratory experiments and electronic structure calculations that the benzene molecule can be formed on Titan's surface in situ via non-equilibrium chemistry by cosmic-ray processing of low-temperature acetylene (C_2H_2) ices. The actual yield of benzene depends strongly on the surface coverage. We suggest that the cosmic-ray-mediated chemistry on Titan's surface could be the dominant source of benzene, i.e., a factor of at least two orders of magnitude higher compared to previously modeled precipitation rates, in those regions of the surface which have a high surface coverage of acetylene

A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase.

A unified low-temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes-polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho-condensed arrangements of fused benzene rings-is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas-phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer-selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free-radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry

On the Synthesis of the Astronomically Elusive 1-Ethynyl-3-Silacyclopropenylidene (c-SiC4H2) Molecule in Circumstellar Envelopes of Carbon-rich Asymptotic Giant Branch Stars and Its Potential Role in the Formation of the Silicon Tetracarbide Chain (SiC4)

Organosilicon molecules such as silicon carbide (SiC), silicon dicarbide (c-SiC2), silicon tricarbide (c-SiC3), and silicon tetracarbide (SiC4) represent basic molecular building blocks connected to the growth of silicon-carbide dust grains in the outflow of circumstellar envelopes of carbon-rich asymptotic giant branch (AGB) stars. Yet, the fundamental mechanisms of the formation of silicon carbides and of the early processes that initiate the coupling of silicon-carbon bonds in circumstellar envelopes have remained obscure. Here, we reveal in a crossed molecular beam experiment contemplated with ab initio electronic calculations that the astronomically elusive 1-ethynyl-3-silacyclopropenylidene molecule (c-SiC4H2, Cs, X1A′) can be synthesized via a single-collision event through the barrierless reaction of the silylidyne radical (SiH) with diacetylene (C4H2). This system represents a benchmark of a previously overlooked class of reactions, in which the silicon-carbon bond coupling can be initiated by a barrierless and overall exoergic reaction between the simplest silicon-bearing radical (silylidyne) and a highly hydrogen-deficient hydrocarbon (diacetylene) in the inner circumstellar envelopes of evolved carbon-rich stars such as IRC+10216. Considering that organosilicon molecules like 1-ethynyl-3-silacyclopropenylidene might be ultimately photolyzed to bare carbon-silicon clusters like the linear silicon tetracarbide (SiC4), hydrogenated silicon-carbon clusters might represent the missing link eventually connecting simple molecular precursors such as silane (SiH4) to the population of silicon-carbide based interstellar grains ejected from carbon-rich AGB stars into the interstellar medium

Absorption Cross Sections of NH_3, NH_2D, NHD_2, and ND_3 in the Spectral Range 140-220 nm and Implications for Planetary Isotopic Fractionation

Cross sections for photoabsorption of NH_3, NH_2D, NHD_2, and ND_3 in the spectral region 140-220 nm were determined at ~298 K using synchrotron radiation. Absorption spectra of NH_2D and NHD_2 were deduced from spectra of mixtures of NH_3 and ND_3, of which the equilibrium concentrations for all four isotopologues obey statistical distributions. Cross sections of NH_2D, NHD_2, and ND_3 are new. Oscillator strengths, an integration of absorption cross sections over the spectral lines, for both A ← X and B ← X systems of NH_3 agree satisfactorily with previous reports; values for NH_2D, NHD_2, and ND_3 agree with quantum chemical predictions. The photolysis of NH_3 provides a major source of reactive hydrogen in the lower stratosphere and upper troposphere of giant planets such as Jupiter. Incorporating the measured photoabsorption cross sections of NH_3 and NH_2D into the Caltech/JPL photochemical diffusive model for the atmosphere of Jupiter, we find that the photolysis efficiency of NH_2D is lower than that of NH_3 by as much as 30%. The D/H ratio in NH_2D/NH_3 for tracing the microphysics in the troposphere of Jupiter is also discussed

Gas-Phase Synthesis of Triphenylene (C18 H12 ).

For the last decades, the hydrogen-abstraction-acetylene-addition (HACA) mechanism has been widely invoked to rationalize the high-temperature synthesis of PAHs as detected in carbonaceous meteorites (CM) and proposed to exist in the interstellar medium (ISM). By unravelling the chemistry of the 9-phenanthrenyl radical ([C14 H9 ]. ) with vinylacetylene (C4 H4 ), we present the first compelling evidence of a barrier-less pathway leading to a prototype tetracyclic PAH - triphenylene (C18 H12 ) - via an unconventional hydrogen abstraction-vinylacetylene addition (HAVA) mechanism operational at temperatures as low as 10 K. The barrier-less, exoergic nature of the reaction reveals HAVA as a versatile reaction mechanism that may drive molecular mass growth processes to PAHs and even two-dimensional, graphene-type nanostructures in cold environments in deep space thus leading to a better understanding of the carbon chemistry in our universe through the untangling of elementary reactions on the most fundamental level

Gas-phase synthesis of benzene via the propargyl radical self-reaction

Polycyclic aromatic hydrocarbons (PAHs) have been invoked in fundamental molecular mass growth processes in our galaxy. We provide compelling evidence of the formation of the very first ringed aromatic and building block of PAHs—benzene—via the self-recombination of two resonantly stabilized propargyl (C3H3) radicals in dilute environments using isomer-selective synchrotron-based mass spectrometry coupled to theoretical calculations. Along with benzene, three other structural isomers (1,5-hexadiyne, fulvene, and 2-ethynyl-1,3-butadiene) and o-benzyne are detected, and their branching ratios are quantified experimentally and verified with the aid of computational fluid dynamics and kinetic simulations. These results uncover molecular growth pathways not only in interstellar, circumstellar, and solar systems environments but also in combustion systems, which help us gain a better understanding of the hydrocarbon chemistry of our universe

Reactivity of the Indenyl Radical (C9 H7 ) with Acetylene (C2 H2 ) and Vinylacetylene (C4 H4 ).

The reactions of the indenyl radicals with acetylene (C2 H2 ) and vinylacetylene (C4 H4 ) is studied in a hot chemical reactor coupled to synchrotron based vacuum ultraviolet ionization mass spectrometry. These experimental results are combined with theory to reveal that the resonantly stabilized and thermodynamically most stable 1-indenyl radical (C9 H7 . ) is always formed in the pyrolysis of 1-, 2-, 6-, and 7-bromoindenes at 1500 K. The 1-indenyl radical reacts with acetylene yielding 1-ethynylindene plus atomic hydrogen, rather than adding a second acetylene molecule and leading to ring closure and formation of fluorene as observed in other reaction mechanisms such as the hydrogen abstraction acetylene addition or hydrogen abstraction vinylacetylene addition pathways. While this reaction mechanism is analogous to the bimolecular reaction between the phenyl radical (C6 H5 . ) and acetylene forming phenylacetylene (C6 H5 CCH), the 1-indenyl+acetylene→1-ethynylindene+hydrogen reaction is highly endoergic (114 kJ mol-1 ) and slow, contrary to the exoergic (-38 kJ mol-1 ) and faster phenyl+acetylene→phenylacetylene+hydrogen reaction. In a similar manner, no ring closure leading to fluorene formation was observed in the reaction of 1-indenyl radical with vinylacetylene. These experimental results are explained through rate constant calculations based on theoretically derived potential energy surfaces

Low-temperature gas-phase formation of indene in the interstellar medium

Polycyclic aromatic hydrocarbons (PAHs) are fundamental molecular building blocks of fullerenes and carbonaceous nanostructures in the interstellar medium and in combustion systems. However, an understanding of the formation of aromatic molecules carrying five-membered rings—the essential building block of nonplanar PAHs—is still in its infancy. Exploiting crossed molecular beam experiments augmented by electronic structure calculations and astrochemical modeling, we reveal an unusual pathway leading to the formation of indene (C9H8)—the prototype aromatic molecule with a five-membered ring—via a barrierless bimolecular reaction involving the simplest organic radical—methylidyne (CH)—and styrene (C6H5C2H3) through the hitherto elusive methylidyne addition–cyclization–aromatization (MACA) mechanism. Through extensive structural reorganization of the carbon backbone, the incorporation of a five-membered ring may eventually lead to three-dimensional PAHs such as corannulene (C20H10) along with fullerenes (C60, C70), thus offering a new concept on the low-temperature chemistry of carbon in our galaxy