Full CI studies of the collinear transition state for the reaction F+H2→HF+H

Abstract

We have performed full CI calculations on the collinear transition state for the reaction F+H2→HF+H. The full CI results are compared with those obtained from single reference and multireference CI calculations and from single reference CPF calculations. In general, only those methods which attempt to account for the effects of higher excitations, such as CPF or CI plus the Davidson correction, yield a transition state location and barrier height in good agreement with the full CI. In an extended basis, the effect of higher excitations is estimated to lower the barrier by as much as 1.5 kcal/mol; such an effect would essentially eliminate the present discrepancy between theory and experiment.