Can the C5H5 + C5H5 → C10H10 → C10H9 + H/C10H8 + H2 Reaction Produce Naphthalene? An Ab Initio/RRKM Study

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2009-09, Vol.113 (36), p.9825-9833
• Main Authors: Mebel, A. M, Kislov, V. V
• Format: Article
• Language: eng ; jpn
• Subjects: A: Kinetics, Spectroscopy
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp905931j

Ab initio and density functional calculations using a variety of theoretical methods (CASSCF, B3LYP, CASPT2, CCSD(T), and G3(MP2,CC)) have been carried out to unravel the mechanism of unimolecular isomerization and dissociation of 9,10-dihydrofulvalene C10H10 (S0) formed by barrierless recombination of two cyclopentadienyl radicals. Different reaction pathways on the C10H10 potential energy surface (PES) are found to lead to the production of 9-H-fulvalenyl radical + H, 9-H-naphthyl radical (a naphthalene precursor) + H, and naphthalene + H2. RRKM calculations of thermal rate constants and product branching ratios at the high pressure limit show that at temperatures relevant to combustion the 9-H-fulvalenyl radical formed by a direct H loss from S0 with endothermicity of 76.3 kcal/mol is expected to be the dominant reaction product. The naphthalene precursor 9,10-dihydronaphthalene (D3) can be produced from the initial S0 adduct by a multistep diradical mechanism involving the formation of a metastable tricyclic diradical intermediate, followed by its three-step opening to a 10-member ring structure, which then undergoes ring contraction producing the naphthalene core structure in D3, with the highest barrier on this pathway being 70.3 kcal/mol. D3 can lose molecular hydrogen producing naphthalene via a barrier of 77.7 kcal/mol relative to the initial adduct. Another possibility is a hydrogen atom elimination in D3 giving rise to the 9-H-naphthyl radical without exit barrier and with overall endothermicity of 59.2 kcal/mol. The pathway to 9-H-naphthyl appears to be preferable as compared to the direct route to 9-H-fulvalenyl at temperatures below 600 K, but the rate constants at these temperatures are too slow for the reaction to be significant. The naphthalene + H2 channel is not viable at any temperature. The following reaction sequence is suggested for kinetic models to account for the recombination of two cyclopentadienyl radicals: c-C 5 H 5 + c-C 5 H 5 → 9,10-dihydrofulvalene → 9-H-fulvalenyl + H ( C 10 H 10 PES ) 9-H-fulvalenyl → naphthalene + H / fulvalene + H ( C 10 H 9 PES ) We conclude that naphthalene can be produced from the recombination of two cyclopentadienyl radicals and is expected to be a favorable product of this reaction sequence at T < 1000 K, but this molecule would be formed through isomerizations and H atom loss on the C10H9 PES (after the initial H elimination from C10H10 S0) and not in conjunction with molecular hydrogen. The alte