On the potential surface dependence of the H + F 2 reaction II. The influence of shoulder- and corner-regions

Abstract

The rotated-morse-cubic-spline/gaussian(RMCS/G) representation of potential energy surfaces is introduced in order to facilitate variations of specific local surface regions. Collinear quantum calculations, and an information theoretic 1D to 3D transformation are reported for the reaction H + F 2(υ = 0) → HF + F using six new potential energy surfaces. These were derived from an extended LEPS surface by variations in either the shoulder region or the corner region, or both. Resulting vibrational product distributions exhibit an increase in (ƒ υ′)both with depending the corner region and with an earlier occurrence of the shoulder. The shapes of the distributions for the non-LEPS surfaces are very similar to the ones obtained for extended LEPS surfaces, and in particular also fail to account for the pronounced wings characteristic of the experimental distributions.