Ultrafast Rydberg-state dissociation in oxygen: Identifying the role of multielectron excitations

Alexander Plunkett, Nathan Harkema, Robert R. Lucchese, C. William McCurdy, Arvinder Sandhu

Research output: Contribution to journalArticlepeer-review

8 Scopus citations


We investigated the fragmentation dynamics of highly excited states of molecular oxygen using femtosecond transient photoelectron spectroscopy. An extreme ultraviolet (XUV) pulse populates the autoionizing Rydberg series converging to O2+cςu-4, and a femtosecond near-infrared (IR) pulse was used to photoionize these states as they dissociate. Monitoring the differential photoelectron spectra as a function of time delay allowed us to obtain the relaxation lifetimes of these Rydberg states. We observed a photoelectron signal corresponding to the formation of a 4p excited atomic oxygen fragment, which is not an expected dissociation product of the (O2+cςu-4)nlσg Rydberg series. Analysis of the time-dependent photoelectron spectra and photoionization calculations indicate that this fragment results from a previously unexplored (O2+Πg4)4p repulsive state and that, contrary to expectations, this multielectron excitation pathway presents a substantial cross section. Our study demonstrates that two-color time-resolved differential photoelectron spectroscopy is an excellent tool to study the fragmentation dynamics of such multielectron excited states, which are not easily probed by other means.

Original languageEnglish (US)
Article number063403
JournalPhysical Review A
Issue number6
StatePublished - Jun 6 2019

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics


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