Reaction mechanism and product branching ratios of the CH + C₃H₈ reaction: a theoretical study.

Abstract

The C4H9 potential energy surface accessed by the reaction of methylidyne radical, CH (X(2)Π), with propane, C3H8, including possible intermediates, transition states and dissociation products, has been studied by ab initio and density functional calculations at the CCSD(T)/CBS//B3LYP/6-311G(d,p) level of theory. The computed relative energies and molecular parameters were utilized to calculate collision-energy-dependent unimolecular rate constants at the zero-pressure limit for isomerization and dissociation channels of the C4H9 adducts formed in the entrance reaction channels. The rate constants were used to evaluate the product branching ratios in the CH + C3H8 reaction under single-collision conditions. The results show that the reaction can produce mostly ethene (C2H4) + ethyl radical (C2H5) and propene (C3H6) + methyl radical (CH3), and up to 14% of various butene isomers (C4H8) + H. The product branching ratios are sensitive to the initial reaction adduct (a butyl radical, C4H9) formed in the entrance channels via barrierless insertion of the CH radical into the terminal and middle C-H bonds of propane or, possibly, into the single C-C bonds. A more definite answer on relative contributions of various available CH insertion channels can be obtained through ab initio quasiclassical trajectory calculations, which are proposed for the future. The results allowed us to conclude that the CH + C3H8 reaction does not result in major amounts in the direct growth of the carbon-skeleton to four-carbon C4H8 products via the CH-for-H exchange because C-C bond cleavages in C4H9 radicals are generally more preferable than C-H bond cleavages.