The spectroscopy of Rydberg to Rydberg transitions in I-2 and Br-2 investigated by vibrationally induced autoionization

MCR Cockett, DA Beattie, NA Macleod, KP Lawley, T Ridley*, RJ Donovan

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Dipole-allowed transitions from vibrationally selected members of the lowest nd Rydberg state cluster in I-2 (n = 5) and Br-2 (n = 4) to autoionizing Rydberg series based on vibrationally excited states of the core are investigated. The photoelectron production spectrum is recorded using delayed field extraction to detect free electrons released by autoionization with up to a few hundred cm(-1) of energy that are subsequently trapped for similar to1mus in the plasma formed at the laser focus. The final state principal quantum numbers typically range from n similar to20-35 and both p and f series can be identified. When one of these core-excited Rydberg state energies coincides with the ionization threshold of a lower vibrational state to within a few cm(-1), a marked increase in the ZEKE-PFI signal is observed, leading to non-Franck-Condon behaviour. Probing the same Rydberg states based on the spin orbit excited core reveals preferential autoionization by electron exchange rather than by vibronic coupling in the p series.

Original languageEnglish
Pages (from-to)1419-1424
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume4
Issue number8
DOIs
Publication statusPublished - 2002

Keywords

  • THRESHOLD PHOTOELECTRON-SPECTROSCOPY
  • ULTRAVIOLET RADIATION
  • ZEKE STATES
  • IONIZATION

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