Unraveling the Origin of Symmetry Breaking in H(2)O@C(60) Endofullerene Through Quantum Computations

We explore the origin of the anomalous splitting of the 1(01) levels reported experimentally for the H(2)O@C(60) endofullerene, in order to give some insight about the physical interpretations of the symmetry breaking observed. We performed fully‐coupled quantum computations within the multiconfiguration time‐dependent Hartree approach employing a rigorous procedure to handle such computationally challenging problems. We introduce two competing physical models, and discuss the observed unconventional quantum patterns in terms of anisotropy in the interfullerene interactions, caused by the change in the off‐center position of the encapsulated water molecules inside the cage or the uniaxial C(60)‐cage distortion, arising from noncovalent bonding upon water's encapsulation, or exohedral fullerene perturbations. Our results show that both scenarios could reproduce the experimentally observed rotational degeneracy pattern, although quantitative agreement with the available experimental rotational levels splitting value has been achieved by the model that considers an uniaxial elongation of the C(60)‐cage. Such finding supports that the observed symmetry breaking could be mainly caused by the distortion of the fullerene cage. However, as nuclear quantum treatments rely on the underlying interactions, a decisive conclusion hinges on the availability of their improved description, taken into account both endofullerene and exohedral environments, from forthcoming highly demanding electronic structure many‐body interaction studies.