Analytical potentials for triatomic molecules

Abstract

Ab initio calculations of the energy have been made at approximately 150 points on the two lowest singlet A′ potential energy surfaces of the water molecule, [Xtilde] 1 A′ and [Btilde] 1 A′, covering structures having D ∞h , C ∞v , C 2v and C s symmetries. The object was to obtain an ab initio surface of uniform accuracy over the whole three-dimensional coordinate space. Molecular orbitals were constructed from a double zeta plus Rydberg basis, and correlation was introduced by single and double excitations from multiconfiguration states which gave the correct dissociation behaviour. A two-valued analytical potential function has been constructed to fit these ab initio energy calculations. The adiabatic energies are given in our analytical function as the eigenvalues of a 2 × 2 matrix, whose diagonal elements define two diabatic surfaces. The off-diagonal element goes to zero for those configurations corresponding to surface intersections, so that our adiabatic surface exhibits the correct Σ/II conical intersections for linear configurations, and singlet/triplet intersections of the O + H2 dissociation fragments. The agreement between our analytical surface and experiment has been improved by using empirical diatomic potential curves in place of those derived from ab initio calculations.