Inclusion of ion-pair states in the diatomics-in-molecules description of potential energy surfaces: van der Waals complexes of HeCl 2 and ArCl 2

Abstract

It is shown that the inclusion of excited ionic configurations in the diatomics-in-molecules (DIM) Hamiltonian serves as a natural means to account for main features of non-additivity in three-body potential energy surfaces of HeCl 2 and ArCl 2 van der Waals complexes. For ground state Cl 2( 1Σ g), while consideration of only neutral configurations leads toT-shaped isomers, inclusion of the excited Cl +Cl −1 configuration stabilizes the linear isomer and destabilizes the T-shaped isomer. Within the same formalism, the excited Cl 2( 3Π) only sustains minima in the T-shaped isomer. Potential energy surfaces created with a minimal DIM basis are constructed and shown to compare favorably with the most accurate ab initio surfaces and experiments. Analytical forms are given for three-body surfaces, meant for fitting purposes and as a convenience in simulations of dynamics.