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

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

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

HACA's Heritage: A Free-Radical Pathway to Phenanthrene in Circumstellar Envelopes of Asymptotic Giant Branch Stars.

The hydrogen-abstraction/acetylene-addition (HACA) mechanism has been central for the last decades in attempting to rationalize the formation of polycyclic aromatic hydrocarbons (PAHs) as detected in carbonaceous meteorites such as in Murchison. Nevertheless, the basic reaction mechanisms leading to the formation of even the simplest tricyclic PAHs like anthracene and phenanthrene are still elusive. Here, by exploring the previously unknown chemistry of the ortho-biphenylyl radical with acetylene, we deliver compelling evidence on the efficient synthesis of phenanthrene in carbon-rich circumstellar environments. However, the lack of formation of the anthracene isomer implies that HACA alone cannot be responsible for the formation of PAHs in extreme environments. Considering the overall picture, alternative pathways such as vinylacetylene-mediated reactions are required to play a crucial role in the synthesis of complex PAHs in circumstellar envelopes of dying carbon-rich stars

HACA's Heritage: A Free-Radical Pathway to Phenanthrene in Circumstellar Envelopes of Asymptotic Giant Branch Stars.

The hydrogen-abstraction/acetylene-addition (HACA) mechanism has been central for the last decades in attempting to rationalize the formation of polycyclic aromatic hydrocarbons (PAHs) as detected in carbonaceous meteorites such as in Murchison. Nevertheless, the basic reaction mechanisms leading to the formation of even the simplest tricyclic PAHs like anthracene and phenanthrene are still elusive. Here, by exploring the previously unknown chemistry of the ortho-biphenylyl radical with acetylene, we deliver compelling evidence on the efficient synthesis of phenanthrene in carbon-rich circumstellar environments. However, the lack of formation of the anthracene isomer implies that HACA alone cannot be responsible for the formation of PAHs in extreme environments. Considering the overall picture, alternative pathways such as vinylacetylene-mediated reactions are required to play a crucial role in the synthesis of complex PAHs in circumstellar envelopes of dying carbon-rich stars

VUV Photoionization Study of the Formation of the Simplest Polycyclic Aromatic Hydrocarbon: Naphthalene (C10H8).

The formation of the simplest polycyclic aromatic hydrocarbon (PAH), naphthalene (C10H8), was explored in a high-temperature chemical reactor under combustion-like conditions in the phenyl (C6H5)-vinylacetylene (C4H4) system. The products were probed utilizing tunable vacuum ultraviolet light by scanning the photoionization efficiency (PIE) curve at a mass-to-charge m/ z = 128 (C10H8+) of molecules entrained in a molecular beam. The data fitting with PIE reference curves of naphthalene, 4-phenylvinylacetylene (C6H5CCC2H3), and trans-1-phenylvinylacetylene (C6H5CHCHCCH) indicates that the isomers were generated with branching ratios of 43.5±9.0 : 6.5±1.0 : 50.0±10.0%. Kinetics simulations agree nicely with the experimental findings with naphthalene synthesized via the hydrogen abstraction-vinylacetylene addition (HAVA) pathway and through hydrogen-assisted isomerization of phenylvinylacetylenes. The HAVA route to naphthalene at elevated temperatures represents an alternative pathway to the hydrogen abstraction-acetylene addition (HACA) forming naphthalene in flames and circumstellar envelopes, whereas in cold molecular clouds, HAVA synthesizes naphthalene via a barrierless bimolecular route

Unconventional gas-phase preparation of the prototype polycyclic aromatic hydrocarbon naphthalene (C 10 H 8 ) via the reaction of benzyl (C 7 H 7 ) and propargyl (C 3 H 3 ) radicals coupled with hydrogen-atom assisted isomerization

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the interstellar medium and in meteorites such as Murchison and Allende and signify the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles (soot particles, interstellar grains). However, the predicted lifetime of interstellar PAHs of some 108 years imply that PAHs should not exist in extraterrestrial environments suggesting that key mechanisms of their formation are elusive. Exploiting a microchemical reactor and coupling these data with computational fluid dynamics (CFD) simulations and kinetic modeling, we reveal through an isomer selective product detection that the reaction of the resonantly stabilized benzyl and the propargyl radicals synthesizes the simplest representative of PAHs - the 10π Hückel aromatic naphthalene (C10H8) molecule - via the novel Propargyl Addition-BenzAnnulation (PABA) mechanism. The gas-phase preparation of naphthalene affords a versatile concept of the reaction of combustion and astronomically abundant propargyl radicals with aromatic radicals carrying the radical center at the methylene moiety as a previously passed over source of aromatics in high temperature environments thus bringing us closer to an understanding of the aromatic universe we live in

VUV Photoionization Study of the Formation of the Simplest Polycyclic Aromatic Hydrocarbon: Naphthalene (C₁₀H₈)

The formation of the simplest polycyclic aromatic hydrocarbon (PAH), naphthalene (C₁₀H₈), was explored in a high-temperature chemical reactor under combustion-like conditions in the phenyl (C₆H₅)–vinylacetylene (C₄H₄) system. The products were probed utilizing tunable vacuum ultraviolet light by scanning the photoionization efficiency (PIE) curve at a mass-to-charge <i>m</i>/<i>z</i> = 128 (C₁₀H₈⁺) of molecules entrained in a molecular beam. The data fitting with PIE reference curves of naphthalene, 4-phenylvinylacetylene (C₆H₅CCC₂H₃), and <i>trans</i>-1-phenylvinylacetylene (C₆H₅CHCHCCH) indicates that the isomers were generated with branching ratios of 43.5±9.0 : 6.5±1.0 : 50.0±10.0%. Kinetics simulations agree nicely with the experimental findings with naphthalene synthesized via the hydrogen abstraction–vinylacetylene addition (HAVA) pathway and through hydrogen-assisted isomerization of phenylvinylacetylenes. The HAVA route to naphthalene at elevated temperatures represents an alternative pathway to the hydrogen abstraction–acetylene addition (HACA) forming naphthalene in flames and circumstellar envelopes, whereas in cold molecular clouds, HAVA synthesizes naphthalene via a barrierless bimolecular route