No abstract

Most large molecules are chiral in their structure: they exist as two enantiomers, which are mirror images of each other. Whereas the rovibronic sublevels of two enantiomers are almost identical (neglecting a minuscular effect of the weak interaction), it turns out that the photoelectric effect is sensitive to the absolute configuration of the ionized enantiomer. Indeed, photoionization of randomly oriented enantiomers by left or right circularly polarized light results in a slightly different electron flux parallel or antiparallel with respect to the photon propagation direction-an effect termed photoelectron circular dichroism (PECD). Our comprehensive study demonstrates that the origin of PECD can be found in the molecular frame electron emission pattern connecting PECD to other fundamental photophysical effects such as the circular dichroism in angular distributions (CDAD). Accordingly, distinct spatial orientations of a chiral molecule enhance the PECD by a factor of about 10.

Photoionization is one of the fundamental light-matter interaction processes in which the absorption of a photon launches the escape of an electron. The time scale of this process poses many open questions. Experiments have found time delays in the attosecond (10−18 seconds) domain between electron ejection from different orbitals, from different electronic bands, or in different directions. Here, we demonstrate that, across a molecular orbital, the electron is not launched at the same time. Rather, the birth time depends on the travel time of the photon across the molecule, which is 247 zeptoseconds (1 zeptosecond = 10−21 seconds) for the average bond length of molecular hydrogen. Using an electron interferometric technique, we resolve this birth time delay between electron emission from the two centers of the hydrogen molecule.

We report on the non-adiabatic offset of the initial electron momentum distribution in the plane of polarization upon single ionization of argon by strong field tunneling and show how to experimentally control the degree of non-adiabaticity. Two-color counter-and co-rotating fields (390 and 780 nm) are compared to show that the non-adiabatic offset strongly depends on the temporal evolution of the laser electric field. We introduce a simple method for the direct access to the non-adiabatic offset using two-color counter-and co-rotating fields. Further, for a single-color circularly polarized field at 780 nm we show that the radius of the experimentally observed donut-like distribution increases for increasing momentum in the light propagation direction. Our observed initial momentum offsets are well reproduced by the strong-field approximation (SFA). A mechanistic picture is introduced that links the measured non-adiabatic offset to the magnetic quantum number of virtually populated intermediate states.

A central motivation for the development of x-ray free-electron lasers has been the prospect of timeresolved single-molecule imaging with atomic resolution. Here, we show that x-ray photoelectron diffraction-where a photoelectron emitted after x-ray absorption illuminates the molecular structure from within-can be used to image the increase of the internuclear distance during the x-ray-induced fragmentation of an O 2 molecule. By measuring the molecular-frame photoelectron emission patterns for a two-photon sequential K-shell ionization in coincidence with the fragment ions, and by sorting the data as a function of the measured kinetic energy release, we can resolve the elongation of the molecular bond by approximately 1.2 a.u. within the duration of the x-ray pulse. The experiment paves the road toward timeresolved pump-probe photoelectron diffraction imaging at high-repetition-rate x-ray free-electron lasers.