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

A three-dimensional potential energy surface is developed to describe the structure and dynamical behavior of the Mg(+)-H(2) 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(+)-H(2) and Mg(+)-D(2) essentially consist of a Mg(+) atomic cation attached, respectively, to a moderately perturbed H(2) or D(2) molecule in a T-shaped configuration with an intermolecular separation of 2.62 Å and a well depth of D(e) = 842  cm(-1). The barrier for internal rotation through the linear configuration is 689  cm(-1). Interaction with the Mg(+) ion is predicted to increase the H(2) molecule's bond-length by 0.008 Å. Variational rovibrational energy level calculations using the new potential energy surface predict a dissociation energy of 614  cm(-1) for Mg(+)-H(2) and 716  cm(-1) for Mg(+)-D(2). The H-H and D-D stretch band centers are predicted to occur at 4059.4 and 2929.2  cm(-1), respectively, overestimating measured values by 3.9 and 2.6  cm(-1). For Mg(+)-H(2) and Mg(+)-D(2), the experimental B and C rotational constants exceed the calculated values by ∼1.3%, suggesting that the calculated potential energy surface slightly overestimates the intermolecular separation. An ab initio dipole moment function is used to simulate the infrared spectra of both complexes.