Potential energy surface and rovibrational calculations for the Mg - H2 and Mg - D2 complexes

Abstract

A three-dimensional potential energy surface is developed to describe the structure and dynamical behavior of the Mg +-H2 and Mg +-D 2 complexes. Ab initio points calculated using the RCCSD(T) method and aug-cc-pVQZ basis set (augmented by bond functions) are fitted using a reproducing kernel Hilbert space method [Ho and Rabitz, J. Chem. Phys. 104, 2584 (1996)] to generate an analytical representation of the potential energy surface. The calculations confirm that Mg +-H2 and Mg +-D2 essentially consist of a Mg + atomic cation attached, respectively, to a moderately perturbed H2 or D2 molecule in a T-shaped configuration with an intermolecular separation of 2.62 and a well depth of De = 842 c..