An improved H3 potential energy surface

Abstract

We report ab initio calculations of the ground state energy for 404 new conformations of H3, supplementing the set of 368 conformations reported previously by others. The entire dataset has been used to constrain an analytical functional form for the potential energy surface, building on that of Truhlar and Horowitz. The new surface extends the Truhlar and Horowitz surface to higher energies and offers some modest improvement at lower energies. In addition, we have eliminated a problem with derivatives of the London equation that was pointed out by Johnson. The new surface matches the 772 ab initio energies with an overall root-mean-square (rms) error of 0.25 mhartree (i.e., 0.16 kcal/mol) and a maximum absolute deviation of 1.93 mhartree (1.21 kcal/mol); for ‘‘noncompact’’ conformations (no interatomic distance smaller than 1.15 bohr), the rms error is 0.17 mhartree (0.11 kcal/mol) and the maximum absolute deviation is 1.10 mhartree (0.69 kcal/mol). The classical barrier height for H+H2→H2+H is estimated to be 15.20±0.15 mhartree (i.e., 9.54±0.09 kcal/mol).