Targeting spectroscopic accuracy for dispersion bound systems from ab initio techniques: Translational eigenstates of Ne@C70.

ABSTRACT

We investigate the endofullerene system Ne@C70 by constructing a three-dimensional Potential Energy Surface (PES) describing the translational motion of the Ne atom. This is constructed from electronic structure calculations from a plethora of methods, including MP2, SCS-MP2, SOS-MP2, RPA@PBE, and C(HF)-RPA, which were previously used for He@C60 in Panchagnula et al. [J. Chem. Phys. 160, 104303 (2024)], alongside B86bPBE-25X-XDM and B86bPBE-50X-XDM. The reduction in symmetry moving from C60 to C70 introduces a double well potential along the anisotropic direction, which forms a test of the sensitivity and effectiveness of the electronic structure methods. The nuclear Hamiltonian is diagonalized using a symmetrized double minimum basis set outlined in Panchagnula and Thom [J. Chem. Phys. 159, 164308 (2023)], with translational energies having error bars ±1 and ±2 cm-1. We find no consistency between electronic structure methods as they find a range of barrier heights and minima positions of the double well and different translational eigenspectra, which also differ from the Lennard-Jones (LJ) PES given in Mandziuk and Bacic [J. Chem. Phys. 101, 2126-2140 (1994)]. We find that generating effective LJ parameters for each electronic structure method cannot reproduce the full PES nor recreate the eigenstates, and this suggests that the LJ form of the PES, while simple, may not be best suited to describe these systems. Even though MP2 and RPA@PBE performed best for He@C60, due to the lack of concordance between all electronic structure methods, we require more experimental data in order to properly validate the choice.