CALCULATIONS ON THE COMPETITION BETWEEN ASSOCIATION AND REACTION FOR C3H++H2

A potential energy surface has been calculated for the competing associative and reactive ion-molecule processes involving the reactants C3H+ + H-2. Our ab initio results show that the linear ion C3H+ and H-2 can directly access the deep potential well of the propargyl ion H2CCCH+, which is calculated to lie 390 kJ mol-1 below the zero-point energy of the reactants. Isomerization between the propargyl ion and the lower energy, CYCliC C3H3+ ion, calculated to lie 501 kJ mol-1 below the zero-point energy of reactants, can subsequently occur via two pathways. One of these pathways involves a transition state lying 22 kJ mol-1 below the energy of the reactants while the other, which occurs at much lower energies, involves two transition states and an intermediate. The dissociation of C-C3H3+ into C-C3H2+ + H is calculated to occur directly, without any intermediate potential energy maximum, but the energy of the products lies 7.3 kJ mol-1 above the energy of the reactants. Using the minimum energy potential pathway and properties of the stationary point structures determined via ab initio methods, we have calculated both the association rate coefficient to produce C3H3+ as a function of density and the branching ratio between the propargyl and cyclic structures of the ion. Our results are in good agreement with some experimental results and in conflict with others. Specifically, we agree with the 1:1 branching ratio measured for the propargyl and cyclic isomers Of C3H3+ at 80 and 300 K and we agree with the rate coefficient for radiative association measured at 80 K. We cannot reproduce reported measurements that the reactive channel (C3H2+ + H) is the dominant channel at 80 K and at low gas densities, or that the association channel at high densities saturates at an effective rate coefficient well below the Langevin value - 2 X 10(-11) CM3 s-1 at 300 K and 1 X 10(-10) cm3 s-1 at 80 K.