The symmetry group paradox for non-rigid molecules

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 betwee...

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Bibliographic Details
Published in:Molecular physics 2017-12, Vol.115 (24), p.3067-3075
Main Author: Dalton, B. J.
Format: Article
Language:English
Subjects:
Configurations
energy level splitting
Energy levels
Enlargement
Group theory
Inversions
Non-rigid molecules
permutation-inversions
Permutations
Quantum theory
Quantum tunnelling
Splitting
Symmetry
symmetry group
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Summary: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.
ISSN:0026-8976
1362-3028
DOI:10.1080/00268976.2017.1347296