We report a fully differential study of ionization of the Ne L-shell by Compton scattering of 20 keV photons. We find two physical mechanisms which modify the Compton-electron emission. Firstly, we observe scattering of the Compton electrons at their parent nucleus. Secondly, we find a distinct maximum in the electron momentum distribution close-to-zero momentum which we attribute to a focusing of the electrons by the Coulomb potential.

We studied strong -field multiphoton ionization of 1-iodo-2-methylbutane enantiomers with 395 nm circularly polarized laser pulses experimentally and theoretically. For randomly oriented molecules, we observe spin polarization up to about 15%, which is independent of the molecular enantiomer. Our experimental findings are explained theoretically as an intricate interplay between three contributions from HOMO, HOMO -1, and HOMO -2, which are formed of 5p -electrons of the iodine atom. For uniaxially oriented molecules, our theory demonstrates even larger spin polarization. Moreover, we predict a sizable enantiosensitive photoelectron circular dichroism of about 10%, which is different for different spin states of photoelectrons.

We experimentally study the influence of the binding energy on nondipole effects in K-shell single-photon ionization of atoms at high photon energies. We find that for each ionization event, as expected by momentum conservation, the photon momentum is transferred almost fully to the recoiling ion. The momentum distribution of the electrons becomes asymmetrically deformed along the photon propagation direction with a mean value of 8/(5c)(E_{γ}-I_{P}) confirming an almost 100 year old prediction by Sommerfeld and Schur [Ann. Phys. (N.Y.) 396, 409 (1930)10.1002/andp.19303960402]. The emission direction of the photoions results from competition between the forward-directed photon momentum and the backward-directed recoil imparted by the photoelectron. Which of the two counteracting effects prevails depends on the binding energy of the emitted electron. As an example, we show that at 20 keV photon energy, Ne^{+} and Ar^{+} photoions are pushed backward towards the radiation source, while Kr^{+} photoions are emitted forward along the light propagation direction.

We investigate experimentally and theoretically the N 1s photoionization of fixed-in-space N-2 molecules at a photon energy of 880 eV. In our experiment, we employed circularly polarized synchrotron radiation for the photoionization and coincident electron and fragment-ion detection using cold target recoil ion momentum spectroscopy. The accompanying angle-resolved calculations were carried out by the multichannel single-center method and code within the frozen-core Hartree-Fock approximation. The computed emission distributions exhibit two distinct features along the molecular axis, which are the results of a superposition of the direct and nearest-neighbor scattering amplitudes for the photoemission from two nitrogen atoms. In the electric-dipole approximation, these peaks are symmetric with respect to both nitrogen atoms. Including nondipole (retardation) effects in the calculations results in a simultaneous increase and decrease of the scattering peaks towards the nitrogen atoms pointing in the forward and backward directions along the light propagation, respectively. These theoretical findings are in agreement with our experimental findings.

We use one-photon excitation to promote K-shell electrons of formic acid (which has a planar equilibrium structure) to an antibonding π* orbital. The excited molecule is known to have a (chiral) pyramidal equilibrium structure. In our experiment, we determine the handedness of the excited molecule by imaging the momenta of charged fragments, which occur after its Coulomb explosion triggered by Auger-Meitner decay cascades succeeding the excitation. We find that the handedness of the excited molecule depends on its spatial orientation with respect to the propagation (or polarization) direction of the exciting photon. The effect is largely independent of the exact polarization properties of the light driving the 1s→π* excitation. Published by the American Physical Society 2024

The differential photoelectron circular dichroism (PECD) of O $1s$ photoelectrons of $R$-trifluoromethyloxirane enantiomers as a function of the photoelectron emission direction in the molecular frame of reference and the direction from which circularly polarized light hits the molecule, is studied experimentally and theoretically for different photoelectron kinetic energies. A coincident detection of the photoelectrons and two ionic molecular fragments, performed with cold target recoil ion momentum spectroscopy, allows us to determine the orientation of the molecule in the laboratory frame and to obtain in addition the molecular-frame photoelectron diffraction patterns. From these we deduce the differential PECD. For given molecular orientations and photoelectron emission directions, we observe a normalized PECD strength clearly beyond 50%. These observations are in agreement with respective relaxed-core Hartree-Fock calculations, performed by employing the single center method. The present results support our recent observation of a huge differential PECD in O $1s$ photoemission of the methyloxirane molecule.

We present a study on molecular-frame photoelectron angular distributions (MFPADs) of small molecules using circularly polarized synchrotron light. We find that the main forward-scattering peaks of the MFPADs are slightly tilted with respect to the molecular axis. This tilt angle is directly connected to the molecular bond length by a simple, universal formula. We apply the derived formula to several examples of MFPADs of C 1s and O 1s photoelectrons of CO, which have been measured experimentally or obtained by means of ab initio modeling. In addition, we discuss the influence of the back-scattering contribution that is superimposed over the analyzed forward-scattering peak in the case of homo-nuclear diatomic molecules such as N-2.

The center of the momentum sphere of O 1s electrons ionized from trifluoromethyloxirane varied between left-circularly and right-circularly polarized light for the particular energies of 3.2, 4.2, and 5.2 eV for unknown reasons.Due to the applied analysis methodology of subtracting the respective data sets, this has erroneously led to significant deviations regarding the determined photoelectron circular dichroism (PECD) at these energies as shown in Fig. 1.The revised PECD values are presented and discussed in light of a recent study on the same target [1].The findings regarding the emitter-site selectivity of inner-shell PECD as the main subject of this paper remain unaltered by this Erratum.We gratefully acknowledge K. Fehre from the University of

We investigate experimentally and theoretically the C and O 1s photoionization of fixed-in-space CO molecules at a photon energy of 905 eV. We find a significant dependence of the photoelectron angular distributions on the direction of propagation of the ionizing radiation. It results from an interplay of nondipole effects, on one hand, and molecular effects, on the other. The nondipole effects lead to an increase of the emission probability in the forward direction along the light propagation, and the photoelectron wave being scattered by the molecular potential gives rise to a strong peak in the direction of the atom neighboring the emitter site. These effects can either conspire or extenuate each other, depending on the photoelectron emission direction and molecular orientation in space.

During the last decade, X-ray free-electron lasers (XFELs) have enabled the study of light-matter interaction under extreme conditions. Atoms which are subject to XFEL radiation are charged by a complex interplay of (several subsequent) photoionization events and electronic decay processes within a few femtoseconds. The interaction with molecules is even more intriguing, since intricate nuclear dynamics occur as the molecules start to dissociate during the charge-up process. Here, we demonstrate that by analyzing photoelectron angular emission distributions and kinetic energy release of charge states of ionic molecular fragments, we can obtain a detailed understanding of the charge-up and fragmentation dynamics. Our novel approach allows for gathering such information without the need of complex ab initio modeling. As an example, we provide a detailed view on the processes happening on a femtosecond time scale in oxygen molecules exposed to intense XFEL pulses.

We investigate the differential ionization probability of chiral molecules in the strong-field regime as a function of the helicity of the incident light. To this end, we analyze the fourfold ionization of bromochlorofluoromethane (CHBrClF) with subsequent fragmentation into four charged fragments and different dissociation channels of the singly ionized methyloxirane. By resolving for the molecular orientation, we show that the photoion circular dichroism signal strength is increased by 2 orders of magnitude.

K. Fehre, G. Nalin, N. M. Novikovskiy, S. Grundmann, G. Kastirke, S. Eckart, F. Trinter, J. Rist, A. Hartung, D. Trabert, Ch. Janke, M. Pitzer, S. Zeller, F. Wiegandt, M. Weller, M. Kircher, M. Hofmann, L. Ph. H. Schmidt, A. Knie, A. Hans, L. Ben Ltaief, A. Ehresmann, R. Berger, H. Fukuzawa, K. Ueda, H. Schmidt-Böcking, J. B. Williams, T. Jahnke, R. Dörner, Ph. V. Demekhin, and M. S. Schöffler Institut für Kernphysik, Goethe-Universität Frankfurt, Max-von-Laue-Straße 1, 60438 Frankfurt am Main, Germany Institut für Physik und CINSaT, Universität Kassel, Heinrich-Plett-Straße 40, 34132 Kassel, Germany Institute of Physics, Southern Federal University, 344090 Rostov-on-Don, Russia 4 Molecular Physics, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany Department of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032 Marburg, Germany Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan Department of Physics, University of Nevada, Reno, Nevada 89557, United States

We report on a joint experimental and theoretical study of photoelectron circular dichroism (PECD) in methyloxirane. By detecting O 1s photoelectrons in coincidence with fragment ions, we deduce the molecule's orientation and photoelectron emission direction in the laboratory frame. Thereby, we retrieve a fourfold differential PECD clearly beyond 50%. This strong chiral asymmetry is reproduced by ab initio electronic structure calculations. Providing such a pronounced contrast makes PECD of fixed-in-space chiral molecules an even more sensitive tool for chiral recognition in the gas phase.

(X-ray) free-electron lasers are employed to site specifically interrogate atomic fragments during ultra-fast photolysis of chiral molecules via time-resolved photoelectron circular dichroism.

Synopsis We investigate the post-collision interaction between a slow electron released by a pump pulse from the neutral helium atom and a fast electron released by a time-delayed probe pulse from the created ion. To this end, we numerically solve the time-dependent Schrödinger equation in the basis of the essential eigenstates of the unperturbed Hamiltonian. We demonstrate that the energy exchange between the slow and the fast electrons and the recapture of slow photoelectrons can be controlled by the properties of the pulse-sequence.

Synopsis The two-photon ionization of the Ne–CH 4 and Ar–SH 4 isoelectronic systems was studied theoretically for the photon energies exceeding the ionization threshold of the outer shells. The calculations demonstrate that the two-photon ionization of the investigated objects is almost entirely a collective process if the one-photon energy corresponds to the energy of the n ℓ → ε ℓ R ′ giant resonance. The largest contribution to the transition (2) amplitude stems from the Auger-like correlation n ℓ 2 → ( 2 ) ε ℓ R ′ 2 ⇒ n ℓ ε ″ ℓ ″ .

Synopsis The spectator resonant interatomic Coulombic decay (SRICD) following the 2s →5p excitation of Ne dimers has been examined experimentally and theoretically. The molecular frame angular distributions (MFADs) of the SRICD electrons depend strongly on the direction of the polarization vector of the exciting photon with respect to the molecular axis. We demonstrate that this effect is caused by the scattering of the low-energy SRICD electron on the density of the spectator electron.

The angular distribution of O 1s photoelectrons emitted from uniaxially oriented methanol is studied experimentally and theoretically. We employed circularly polarized photons of an energy of hν = 550 eV for our investigations. We measured the three-dimensional photoelectron angular distributions of methanol, with the CH3–OH axis oriented in the polarization plane, by means of cold target recoil ion momentum spectroscopy. The experimental results are interpreted by single active electron calculations performed with the single center method. A comparative theoretical study of the respective molecular-frame angular distributions of O 1s photoelectrons of CO, performed for the same photoelectron kinetic energy and for a set of different internuclear distances, allows for disentangling the role of internuclear distance and the hydrogen atoms of methanol as compared to carbon monoxide.

We investigate K-shell ionization of N_{2} at 40 keV photon energy. Using a cold target recoil ion momentum spectroscopy reaction microscope, we determine the vector momenta of the photoelectron, the Auger electron, and both N^{+} fragments. These fully differential data show that the dissociation process of the N_{2}^{2+} ion is significantly modified not only by the recoil momentum of the photoelectron but also by the photon momentum and the momentum of the emitted Auger electron. We find that the recoil energy introduced by the photon and the photoelectron momentum is partitioned with a ratio of approximately 30∶70 between the Auger electron and fragment ion kinetic energies, respectively. We also observe that the photon momentum induces an additional rotation of the molecular ion.

We investigate angular emission distributions of the 1s photoelectrons of N_{2} ionized by linearly polarized synchrotron radiation at hν=40  keV. As expected, nondipole contributions cause a very strong forward-backward asymmetry in the measured emission distributions. In addition, we observe an unexpected asymmetry with respect to the polarization direction, which depends on the direction of the molecular fragmentation. In particular, photoelectrons are predominantly emitted in the direction of the forward nitrogen atom. This observation cannot be explained via asymmetries introduced by the initial bound and final continuum electronic states of the oriented molecule. The present simulations assign this asymmetry to a novel nontrivial effect of the recoil imposed to the nuclei by the fast photoelectrons and high-energy photons, which results in a propensity for the ions to break up along the axis of the recoil momentum. The results are of particular importance for the interpretation of future experiments at x-ray free electron lasers operating in the few tens of keV regime, where such nondipole and recoil effects will be essential.