A Spectroscopic Validation of the Improved Lennard–Jones Model

Abstract

The Lennard–Jones (LJ) and Improved Lennard–Jones (ILJ) potential models have been deeply tested on the most accurate CCSD(T)/CBS electronic energies calculated for some weakly bound prototype systems. These results are important to plan the correct application of such models to systems at increasing complexity. CCSD(T)/CBS ground state electronic energies were determined for 21 diatomic systems composed by the combination of the noble gas atoms. These potentials were employed to calculate the rovibrational spectroscopic constants, and the results show that for 20 of the 21 pairs the ILJ predictions agree more effectively with the experimental data than those of the LJ model. The CCSD(T)/CBS energies were also used to determine the β parameter of the ILJ form, related to the softness/hardness of the interacting partners and controlling the shape of the potential well. This information supports the experimental finding that suggests the adoption of β≈9 for most of the systems involving noble gas atoms. The He-Ne and He-Ar molecules have a lifetime of less than 1ps in the 200–500 K temperature range, indicating that they are not considered stable under thermal conditions of gaseous bulks. Furthermore, the controversy concerning the presence of a “virtual” or a “real” vibrational state in the He2 molecule is discussed.