Quantum Defect Theory for Molecules
During the past 15 years, the developments of molecular quantum defect theory and of the high-resolution spectroscopy of molecular Rydberg states have run largely parallel and have mutually stimulated each other. Before 1970, only moderately high molecular Rydberg states had been observed whose effective principal quantum numbers ranged typically from 2 to 6. The most complete observations were made for H 2 and NO. 1.2 Mulliken 3, in a famous series of papers which appeared in the sixties, summarized the knowledge of Rydberg states in molecules and gave a detailed conceptual description of their electronic and fine structures. He discussed in particular how the electronic wavefunction of a diatomic Rjdberg system evolves through various stages when the nuclei move adiabatically farther and farther apart. While the structures of the low Rydberg states showed many interesting features reflecting the beginning uncoupling of the Rydberg electron from the nuclear framework as well as interactions with valence states, it was not obvious how these states would be related to the scattering or continuum states observed in collision or photionization experiments.
KeywordsPotential Energy Curve Rydberg State Ionization Threshold Quantum Defect Rydberg Series
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