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

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 O-2(+) c(4)Sigma(-)(u), 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 (O-2(+) c(4)Sigma(-)(u))nl sigma(g) Rydberg series. Analysis of the time-dependent photoelectron spectra and photoionization calculations indicate that this fragment results from a previously unexplored (O-2(+) (4)Pi(g))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.US Army Research Laboratory; U.S. Army Research Office [W911NF-14-1-0383]; National Science Foundation (NSF) [PHY-1505556]; U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) [DE-SC0018251]; US Department of Energy Chemical Sciences, Geosciences, and Biosciences Division [DE-AC02-05CH11231]This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at repository@u.library.arizona.edu