Caged-electron states and split-electron states in the endohedral alkali C₆₀

The low-lying electronic states of neutral X@C60 (X = Li, Na, K, Rb) have been computed and analyzed by employing state-of-the-art high level many-electron methods. Apart from the common charge-separated states, well known to be present in endohedral fullerenes, one non-charge-separated state has been found in each of the investigated systems. In Li@C60 and Na@C60, the non-charge-separated state is a caged-electron state already discussed before for Li@C60. This indicates that the application of this low-lying state of Li@C60 discussed before is also applicable for Na@C60. In K@C60 and Rb@C60, the electronic radial distribution analysis shows that this hitherto unknown non-charge-separated state possesses a different nature from that of a caged-electron state.