Quasiclassical trajectory calculations of the reaction C+C2H2 -> l-C3H, c-C3H+H, C-3+H-2 using full-dimensional triplet and singlet potential energy surfaces

Abstract

Full-dimensional, density functional theory (B3LYP/6-311g(d,p))-based potential energy surfaces (PESs) are reported and used in quasi-classical calculations of the reaction of C with C2H2. For the triplet case, the PES spans the region of the reactants, the complex region (with numerous minima and saddle points) and the products, linear(l)-C 3H+H, cyclic(c)-C3H+H and c-3C 3+H2. For the singlet case, the PES describes the complex region and products l-C3H+H, c-C3H+H and l- 1C3 +H2. The PESs are invariant under permutation of like nuclei and are fit to tens of thousands of electronic energies. Energies and harmonic frequencies of the PESs agree well the DFT ones for all stationary points and for the reactant and the products. Dynamics calculations on the triplet PES find both l-C3H and c-C3H products, with l-C3H being dominant at the energies considered. Limited unimolecular reaction dynamics on the singlet PES find both products in comparable amounts as well as the C3+H2 product. ？ 2006 American Institute of Physics.