Shape resonances play a central role in many areas of science, but the real-time measurement of the associated many-body dynamics remains challenging. Here, we present measurements of recoil frame angle-resolved photoionization delays in the vicinity of shape resonances of CF 4 . This technique provides insights into the spatiotemporal photoionization dynamics of molecular shape resonances. We find delays of up to ∼600 as in the ionization out of the highest occupied molecular orbital (HOMO) with a strong dependence on the emission direction and a pronounced asymmetry along the dissociation axis. Comparison with quantum-scattering calculations traces the asymmetries to the interference of a small subset of partial waves at low kinetic energies and, additionally, to the interference of two overlapping shape resonances in the HOMO-1 channel. Our experimental and theoretical results establish a broadly applicable approach to space-and time-resolved photoionization dynamics in the molecular frame.

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We present a combined experimental and theoretical investigation of the electron dynamics and body-frame angular dependence of valence photo-single ionization of CF 4 and subsequent dissociation into CF + 3 and F. Ionization from a valence t 2 orbital shows overlapping shape resonances close to threshold that couple to the same total symmetry, leading to striking quantum interference effects that can be seen in the recoil-frame photoelectron angular distributions.