Terahertz spectroscopy of the helium endofullerene He@C₆₀

We studied the quantized translational motion of single He atoms encapsulated in molecular cages by terahertz absorption. The temperature dependence of the THz absorption spectra of ³He@C₆₀ and ⁴He@C₆₀ crystal powder samples was measured between 5 and 220 K. At 5 K there is an absorption line at 96.8 cm^-1 (2.90 THz) in ³He@C₆₀ and at 81.4 cm (2.44 THz) in ⁴He@C₆₀, while additional absorption lines appear at higher temperature. An anharmonic spherical oscillator model with a displacement-induced dipole moment was used to model the absorption spectra. Potential energy terms with powers of two, four and six and induced dipole moment terms with powers one and three in the helium atom displacement from the fullerene cage center were sufficient to describe the experimental results. Excellent agreement is found between potential energy functions derived from measurements on the ³He and ⁴He isotopes. One absorption line corresponds to a three-quantum transition in ⁴He@C₆₀, allowed by the anharmonicity of the potential function and by the non-linearity of the dipole moment in He atom displacement. The potential energy function of icosahedral symmetry does not explain the fine structure observed in the low temperature spectra.