Strong vibronic coupling in molecular Rydberg states

Robert L. Whetten, Edward R. Grant

Research output: Contribution to journalArticlepeer-review


We consider the vibronic properties of molecular Rydberg states in the strong coupling (degenerate) limit of the ion core, and show how the observed optical Rydberg spectrum for such a molecule is closely related to the Franck-Condon spectrum of its Jahn-Teller ion core, regardless of the symmetry labels attached to the Rydberg electronic species. These relationships permit the resolution of a quarter-century old paradox in the Rydberg spectrum of benzene and give rise to easily verifiable predictions concerning benzene's vibronic spectrum, which are applied to a recently discovered new Rydberg series. We further suggest that observed deviations from the idealized Rydberg case discussed here will reveal additional details about the coupling of Rydberg electronic and core-vibronic motion.

Original languageEnglish (US)
Pages (from-to)5999-6005
Number of pages7
JournalThe Journal of Chemical Physics
Issue number12
StatePublished - 1983
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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