Adam Trevitt

Chemically activated reactions on the C7H5 energy surface: Propargyl + diacetylene, i-C5H3 + acetylene, and n-C5H3 + acetylene

Gabriel da Silva et al. — Thu, 09 Feb 2012 16:12:04 PST

This study uses computational chemistry and statistical reaction rate theory to investigate the chemically activated reaction of diacetylene (butadiyne, C4H2) with the propargyl radical (C •H2CCH) and the reaction of acetylene (C 2H2) with the i-C5H3 (CH 2CCCC•H) and n-C5H3 (CHCC •HCCH) radicals. A detailed G3SX-level C7H 5 energy surface demonstrates that the C3H3 + C4H2 and C5H3 + C2H 2 addition reactions proceed with moderate barriers, on the order of 10 to 15 kcal mol-1, and form activated open-chain C 7H5 species that can isomerize to the fulvenallenyl radical with the highest barrier still significantly below the entrance channel energy. Higher-energy pathways are available leading to other C 7H5 isomers and to a number of C7H4 species + H. Rate constants in the large multiple-well (15) multiple-channel (30) chemically activated system are obtained from a stochastic solution of the one-dimensional master equation, with RRKM theory for microcanonical rate constants. The dominant products of the C4H2 + C 3H3 reaction at combustion-relevant temperatures and pressures are i-C5H3 + C2H2 and CH2CCHCCCCH + H, along with several quenched C7H 5 intermediate species below 1500 K. The major products in the n-C5H3 + C2H2 reaction are i-C 5H3 + C2H2 and a number of C 7H4 species + H, with C7H5 radical stabilization at lower temperatures. The i-C5H3 + C 2H2 reaction predominantly leads to C7H 4 + H and to stabilized C7H5 products. The title reactions may play an important role in polycyclic aromatic hydrocarbon (PAH) formation in combustion systems. The C7H5 potential energy surface developed here also provides insight into several other important reacting gas-phase systems relevant to combustion and astrochemistry, including C2H + the C3H4 isomers propyne and allene, benzyne + CH, benzene + C(3P), and C7H5 radical decomposition, for which some preliminary analysis is presented. © 2011 the Owner Societies.

Products of the Benzene + O(3P) Reaction

Craig A. Taatjes et al. — Thu, 09 Feb 2012 16:12:01 PST

Reaction of the C2H radical with 1-Butyne (C4H6): Low Temperature Kinetics and Isomer-Specific Product Detection

Satchin Soorkia et al. — Thu, 09 Feb 2012 16:11:58 PST

Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

Adam J. Trevitt et al. — Thu, 09 Feb 2012 16:11:55 PST

Low-temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165, and 295 K is found to be relatively constant over this temperature range, (3.9−4.9) × 10−10 cm3 molecule−1 s−1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a rate coefficient of 1.3 × 10−10 cm3 molecule−1 s−1 at 105 K. At room temperature, nonexponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta, and para isomers of cyanotoluene because of their similar ionization energies and the 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn’s moon Titan (100 K) and are also likely to proceed at the temperature of interstellar clouds (10−20 K).

Reactions of simple and peptidic alpha-carboxylate radical anions with dioxygen in the gas phase

Tony Ly et al. — Thu, 09 Feb 2012 16:11:52 PST

α-Carboxylate radical anions are potential reactive intermediates in the free radical oxidation of biological molecules (e.g., fatty acids, peptides and proteins). We have synthesised well-defined α-carboxylate radical anions in the gas phase by UV laser photolysis of halogenated precursors in an ion-trap mass spectrometer. Reactions of isolated acetate (CH2CO 2-) and 1-carboxylatobutyl (CH3CH 2CH2CHCO2-) radical anions with dioxygen yield carbonate (CO3-) radical anions and this chemistry is shown to be a hallmark of oxidation in simple and alkyl-substituted cross-conjugated species. Previous solution phase studies have shown that Cα-radicals in peptides, formed from free radical damage, combine with dioxygen to form peroxyl radicals that subsequently decompose into imine and keto acid products. Here, we demonstrate that a novel alternative pathway exists for two α-carboxylate Cα-radical anions: the acetylglycinate radical anion (CH3C(O)NHCHCO2-) and the model peptide radical anion, YGGFG-. Reaction of these radical anions with dioxygen results in concerted loss of carbon dioxide and hydroxyl radical. The reaction of the acetylglycinate radical anion with dioxygen reveals a two-stage process involving a slow, followed by a fast kinetic regime. Computational modelling suggests the reversible formation of the Cα peroxyl radical facilitates proton transfer from the amide to the carboxylate group, a process reminiscent of, but distinctive from, classical proton-transfer catalysis. Interestingly, inclusion of this isomerization step in the RRKM/ME modelling of a G3SX level potential energy surface enables recapitulation of the experimentally observed two-stage kinetics. © 2011 the Owner Societies