ABSTRACT
In many situations, the energy levels for a quantum system, whose Hamiltonian is invariant under a specific symmetry group, are split when the Hamiltonian is replaced by a new one with lower symmetry. In non-rigid molecules (NRM), fast quantum tunnelling processes allow the molecule to change between different geometrical configurations related by permutations of identical nuclei (or with inversion as well), resulting in the splitting of the energy levels for the rigid molecule (RM) case where tunnelling is absent. However, for NRM, there is apparently a paradoxical situation where although the original RM energy levels are associated with a symmetry group isomorphic to the point group for the geometrical configuration, the split NRM energy levels are associated with a symmetry group consisting of all permutations and inversions related to the fast quantum tunnelling processes between configurations, and for which the point group is a subgroup. The resolution of this paradox, where energy level splitting is evidently accompanied by an enlargement of the symmetry group, is the subject of this article.
Acknowledgments
The author acknowledges correspondence with G.A. Natanson, whose 1985 paper drew his attention to the symmetry group paradox. A helpful suggestion by a referee is also acknowledged.
Disclosure statement
No potential conflict of interest was reported by the author.