Selective control over fragmentation reactions in polyatomic molecules using impulsive laser alignment

We investigate the possibility of using molecular alignment for controlling the relative probability of individual reaction pathways in polyatomic molecules initiated by electronic processes on the few-femtosecond time scale. Using acetylene as an example, it is shown that aligning the molecular axis with respect to the polarization direction of the ionizing laser pulse does not only allow us to enhance or suppress the overall fragmentation yield of a certain fragmentation channel but, more importantly, to determine the relative probability of individual reaction pathways starting from the same parent molecular ion. We show that the achieved control over dissociation or isomerization pathways along specific nuclear degrees of freedom is based on a controlled population of associated excited dissociative electronic states in the molecular ion due to relatively enhanced ionization contributions from inner valence orbitals.FWN – Publicaties zonder aanstelling Universiteit Leide

Recovery of High Energy Photoelectron Circular Dichroism through Fano Interference

It is commonly accepted that the magnitude of a photoelectron circular dichroism (PECD) is governed by the ability of an outgoing photoelectron wave packet to probe the chiral asymmetry of a molecule. To be able to accumulate this characteristic asymmetry while escaping the chiral ion, photoelectrons need to have relatively small kinetic energies of up to a few tens of electron volts. Here, we demonstrate a substantial PECD for very fast photoelectrons above 500 eV kinetic energy released from methyloxirane by a participator resonant Auger decay of its lowermost O 1s excitation. This effect emerges as a result of the Fano interference between the direct and resonant photoionization pathways, notwithstanding that their individual effects are negligibly small. The resulting dichroic parameter has an anomalous dispersion: It changes its sign across the resonance, which can be considered as an analogue of the Cotton effect in the x-ray regime

Separating Dipole and Quadrupole Contributions to Single Photon Double Ionization

We report on a kinematically complete measurement of double ionization of helium by a single 1100 eV circularly polarized photon. By exploiting dipole selection rules in the two-electron continuum state, we observed the angular emission pattern of electrons originating from a pure quadrupole transition. Our fully differential experimental data and companion ab initio nonperturbative theory show the separation of dipole and quadrupole contributions to photo-double-ionization and provide new insight into the nature of the quasifree mechanism.Comment: 5 Pages, 3 Figure

Born in weak fields below threshold photoelectron dynamics

We investigate the dynamics of ultra-low kinetic energy photoelectrons. Many experimental techniques employed for the detection of photoelectrons require the presence of (more or less) weak electric extraction fields in order to perform the measurement. Our studies show that ultra-low energy photoelectrons exhibit a characteristic shift in their apparent measured momentum when the target system is exposed to such static electric fields. Already fields as weak as 1 V cm(-1) have an observable influence on the detected electron momentum. This apparent shift is demonstrated by an experiment on zero energy photoelectrons emitted from He and explained through theoretical model calculations

Kinematically complete experimental study of Compton scattering at helium atoms near the threshold

Compton scattering is one of the fundamental interaction processes of light with matter. When discovered1, it was described as a billiard-type collision of a photon ‘kicking’ a quasi-free electron. With decreasing photon energy, the maximum possible momentum transfer becomes so small that the corresponding energy falls below the binding energy of the electron. In this regime, ionization by Compton scattering becomes an intriguing quantum phenomenon. Here, we report on a kinematically complete experiment studying Compton scattering off helium atoms in that regime. We determine the momentum correlations of the electron, the recoiling ion and the scattered photon in a coincidence experiment based on cold target recoil ion momentum spectroscopy, finding that electrons are not only emitted in the direction of the momentum transfer, but that there is a second peak of ejection to the backward direction. This finding links Compton scattering to processes such as ionization by ultrashort optical pulses2, electron impact ionization3,4, ion impact ionization5,6 and neutron scattering7, where similar momentum patterns occur. © 2020, The Author(s), under exclusive licence to Springer Nature Limited