Structural, Spectroscopic, and Dynamic Properties of Li2+(X2∑g+) in Interaction with Krypton Atom.

Abstract

We report a computational study of the potential energy surface (PES) and vibrational bound states for the ground electronic state of Li2+Kr. The PES was calculated in Jacobi coordinates at the Restricted Coupled Cluster method RCCSD(T) level of calculation and using aug-cc-pVnZ (n = 4 and 5) basis sets. Afterward, this PES is extrapolated to the complete basis set (CBS) limit for correction. The obtained interaction energies were, then, interpolated numerically using the reproducing kernel Hilbert space polynomial (RKHS) approach to produce analytic expressions for the 2D-PES. The analytical PES is used to solve the nuclear Schrodinger equation to determine the bound states' eigenvalues of Li2+Kr for a J = 0 total angular momentum configuration and to understand the effects of orientational anisotropy of the forces and the interplay between the repulsive and attractive interaction within the potential surface. In addition, the radial and angular distributions of some selected bound state levels, which lie below, around, and above the T-shaped 90° barrier well, are calculated and discussed. We note that the radial distributions clearly acquire a more complicated nodal structure and correspond to bending and stretching vibrational motions "mode" of the Kr atom along the radial coordinate, and the situation becomes very different at the highest bound states levels with energies higher than the T-shaped 90° barrier well. The shape of the distributions becomes even more complicated, with extended angular distributions and prominent differences between even and odd states.