Fully Coupled Quantum Treatment of Nanoconfined Systems: A Water Molecule inside a Fullerene C₆₀

We implemented a systematic procedure for treating the quantal rotations by including all translational and vibrational degrees of freedom for any triatomic bent molecule in any embedded or confined environment, within the MCTDH framework. Fully coupled quantum treatments were employed to investigate unconventional properties in nanoconfined molecular systems. In this way, we facilitate a complete theoretical analysis of the underlying dynamics that enables us to compute the energy levels and the nuclear spin isomers of a single water molecule trapped in a C₆₀ fullerene cage. The key point lies in the full 9D description of both nuclear and electronic degrees of freedom, as well as a reliable representation of the guest-host interaction. The presence of occluded impurities or inhomogeneities due to noncovalent interactions in the interfullerene environment could modify aspects of the potential, causing significant coupling between otherwise uncoupled modes. Using specific n-mode model potentials, we obtained splitting patterns that confirm the effects of symmetry breaking observed by experiments in the ground ortho-H₂O state. Further, our investigation reveals that the first rotationally excited states of the encapsulated ortho- and para-H₂O have also raised their 3-fold degeneracy. In view of the complexity of the problem, our results highlight the importance of accurate and computational demanding approaches for building up predictive models for such nanoconfined molecules.