Normalized kinetic field potentials for the atom‐diatom reactions. Testing the collinear surfaces

The method of constructing the potential energy surface ( W W ) for the collinear atom‐diatom chemical reactions, via the virial theorem from the normalized rotating Morse function (rotated around the united atom) representation (T‐RMF) of the electronic kinetic energy, T , is tested by generating various W W surfaces for the H + H—H → H—H + H and F + H—H → F—H + H collinear reactions, and comparing them with the corresponding ab initio (H 3 ) and LEPS (FHH) surfaces. To obtain the T‐RMF parameters, only a knowledge of the coordinates and energy along the zero‐virial path (zvp) is required, W W = W W [ZVP]. Two approximations of the ZVP have been used: an analytical fit of the ab initio steepest descent minimum energy path (MEP), and the bond energy/bond order (BEBO) path. Tests of both the W T [MEP] and W W [BEBO] surfaces suggest considerable utility of the T‐RMF approach in which the virial theorem and the so called T‐normalization condition are employed to a priori control the valleys curvature variations during reaction. A notable feature of the H 3 W W model surfaces is a relatively good representation of the repulsive wall of the surface.