Translational eigenstates of He@C${}_{60}$ from four-dimensional \textit{ab initio} Potential Energy Surfaces interpolated using Gaussian Process Regression

Abstract

We investigate the endofullerene system ${}^3$He@C${}_{60}$ with a four-dimensional Potential Energy Surface (PES) to include the three He translational degrees of freedom and C${}_{60}$ cage radius. We compare MP2, SCS-MP2, SOS-MP2, RPA@PBE and C(HF)-RPA to calibrate and gain confidence in the choice of electronic structure method. Due to the high cost of these calculations, the PES is interpolated using Gaussian Process Regression (GPR), owing to its effectiveness with sparse training data. The PES is split into a two-dimensional radial surface, to which corrections are applied to achieve an overall four-dimensional surface. The nuclear Hamiltonian is diagonalised to generate the in-cage translational/vibrational eigenstates. The degeneracy of the three-dimensional harmonic oscillator energies with principal quantum number $n$ is lifted due to the anharmonicity in the radial potential. The $(2l+1)$-fold degeneracy of the angular momentum states is also weakly lifted, due to the angular dependence in the potential. We calculate the fundamental frequency to range between 96cm${}^{-1}$ and 110cm${}^{-1}$ depending on the electronic structure method used. Error bars of the eigenstate energies were calculated from the GPR and are on the order of approximately $\pm$ 1.5cm${}^{-1}$. Wavefunctions are also compared by considering their overlap and Hellinger distance to the one-dimensional empirical potential. As with the energies, the two \textit{ab initio} methods MP2 and RPA@PBE show the best agreement. While MP2 has better agreement than RPA@PBE, due to its higher computational efficiency and comparable performance, we recommend RPA as an alternative electronic structure method of choice to MP2 for these systems.

arXiv comment14 pages, 5 figures; SI 6 pages, 4 figures. JCP Accepted version

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