Role of the Binding Energy on Nondipole Effects in Single-Photon Ionization.

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.

Tracing Photoinduced Hydrogen Migration in Alcohol Dications from Time-Resolved Molecular-Frame Photoelectron Angular Distributions.

The recent implementation of attosecond and few-femtosecond X-ray pump/X-ray probe schemes in large-scale free-electron laser facilities has opened the way to visualize fast nuclear dynamics in molecules with unprecedented temporal and spatial resolution. Here, we present the results of theoretical calculations showing how polarization-averaged molecular-frame photoelectron angular distributions (PA-MFPADs) can be used to visualize the dynamics of hydrogen migration in methanol, ethanol, propanol, and isopropyl alcohol dications generated by X-ray irradiation of the corresponding neutral species. We show that changes in the PA-MFPADs with the pump-probe delay as a result of intramolecular photoelectron diffraction carry information on the dynamics of hydrogen migration in real space. Although visualization of this dynamics is more straightforward in the smaller systems, methanol and ethanol, one can still recognize the signature of that motion in propanol and isopropyl alcohol and assign a tentative path to it. A possible pathway for a corresponding experiment requires an angularly resolved detection of photoelectrons in coincidence with molecular fragment ions used to define a molecular frame of reference. Such studies have become, in principle, possible since the first XFELs with sufficiently high repetition rates have emerged. To further support our findings, we provide experimental evidence of H migration in ethanol-OD from ion-ion coincidence measurements performed with synchrotron radiation.

Ångstrom-Depth Resolution with Chemical Specificity at the Liquid-Vapor Interface.

The determination of depth profiles across interfaces is of primary importance in many scientific and technological areas. Photoemission spectroscopy is in principle well suited for this purpose, yet a quantitative implementation for investigations of liquid-vapor interfaces is hindered by the lack of understanding of electron-scattering processes in liquids. Previous studies have shown, however, that core-level photoelectron angular distributions (PADs) are altered by depth-dependent elastic electron scattering and can, thus, reveal information on the depth distribution of species across the interface. Here, we explore this concept further and show that the experimental anisotropy parameter characterizing the PAD scales linearly with the average distance of atoms along the surface normal obtained by molecular dynamics simulations. This behavior can be accounted for in the low-collision-number regime. We also show that results for different atomic species can be compared on the same length scale. We demonstrate that atoms separated by about 1 Å along the surface normal can be clearly distinguished with this method, achieving excellent depth resolution.

Vibrationally Resolved Inner-Shell Photoexcitation of the Molecular Anion C2.

Carbon 1s core-hole excitation of the molecular anion C2 - has been experimentally studied at high resolution by employing the photon-ion merged-beams technique at a synchrotron light source. The experimental cross section for photo-double-detachment shows a pronounced vibrational structure associated with 1 σ u → 3 σ g ${1\sigma _u \to 3\sigma _g }$ and 1 σ g → 1 π u ${1\sigma _g \to 1\pi _u }$ core excitations of the C2 - ground level and first excited level, respectively. A detailed Franck-Condon analysis reveals a strong contraction of the C2 - molecular anion by 0.2 Šupon this core photoexcitation. The associated change of the molecule's moment of inertia leads to a noticeable rotational broadening of the observed vibrational spectral features. This broadening is accounted for in the present analysis which provides the spectroscopic parameters of the C2 - 1 σ u - 1 3 σ g 2 2 Σ u + ${1\sigma _u^{ - 1} \,3\sigma _g^2 \;^2 \Sigma _u^ + }$ and 1 σ g - 1 3 σ g 2 2 Σ g + ${1\sigma _g^{ - 1} \,3\sigma _g^2 \;^2 \Sigma _g^ + }$ core-excited levels.

High-energy molecular-frame photoelectron angular distributions: a molecular bond-length ruler.

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 N2.

Ion and Electron Momentum Distributions from Single and Double Ionization of Helium Induced by Compton Scattering.

We present the momentum distributions of the nucleus and of the electrons from double ionization of the helium atom by Compton scattering of photons with hν=40 keV. We find that the doubly charged ion momentum distribution is very close to the Compton profile of the nucleus in the ground state of the helium atom, and the momentum distribution of the singly charged ion to give a precise image of the electron Compton profile. To reproduce these results, nonrelativistic calculations require the use of highly correlated initial- and final-state wave functions.

Observation of Nondipole-Induced Asymmetry in the Angular Emission Distribution of Photoelectrons from Fixed-in-Space CO Molecules.

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.

Fourfold Differential Photoelectron Circular Dichroism.

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.

Photon Momentum Transfer in Single-Photon Double Ionization of Helium.

We theoretically and experimentally investigate the photon momentum transfer in single-photon double ionization of helium at various large photon energies. We find that the forward shifts of the momenta along the light propagation of the two photoelectrons are roughly proportional to their fraction of the excess energy. The mean value of the forward momentum is about 8/5 of the electron energy divided by the speed of light. This holds for fast and slow electrons despite the fact that the energy sharing is highly asymmetric and the slow electron is known to be ejected by secondary processes of shake off and knockout rather than directly taking its energy from the photon. The biggest deviations from this rule are found for the region of equal energy sharing where the quasifree mechanism dominates double ionization.

Multiple Photodetachment of Carbon Anions via Single and Double Core-Hole Creation.

We report on new measurements of m-fold photodetachment (m=2-5) of carbon anions via K-shell excitation and ionization. The experiments were carried out employing the photon-ion merged-beams technique at a synchrotron light source. While previous measurements were restricted to double detachment (m=2) and to just the lowest-energy K-shell resonance at about 282 eV, our absolute experimental m-fold detachment cross sections at photon energies of up to 1000 eV exhibit a wealth of new thresholds and resonances. We tentatively identify these features with the aid of detailed atomic-structure calculations. In particular, we find unambiguous evidence for fivefold detachment via double K-hole production.

Resonant Auger decay driving intermolecular Coulombic decay in molecular dimers.

In 1997, it was predicted that an electronically excited atom or molecule placed in a loosely bound chemical system (such as a hydrogen-bonded or van-der-Waals-bonded cluster) could efficiently decay by transferring its excess energy to a neighbouring species that would then emit a low-energy electron. This intermolecular Coulombic decay (ICD) process has since been shown to be a common phenomenon, raising questions about its role in DNA damage induced by ionizing radiation, in which low-energy electrons are known to play an important part. It was recently suggested that ICD can be triggered efficiently and site-selectively by resonantly core-exciting a target atom, which then transforms through Auger decay into an ionic species with sufficiently high excitation energy to permit ICD to occur. Here we show experimentally that resonant Auger decay can indeed trigger ICD in dimers of both molecular nitrogen and carbon monoxide. By using ion and electron momentum spectroscopy to measure simultaneously the charged species created in the resonant-Auger-driven ICD cascade, we find that ICD occurs in less time than the 20 femtoseconds it would take for individual molecules to undergo dissociation. Our experimental confirmation of this process and its efficiency may trigger renewed efforts to develop resonant X-ray excitation schemes for more localized and targeted cancer radiation therapy.

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.

Photon-Momentum-Induced Molecular Dynamics in Photoionization of N_{2} at hν=40 keV.

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.

Recoil-Induced Asymmetry of Nondipole Molecular Frame Photoelectron Angular Distributions in the Hard X-ray Regime.

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.

Determination of Interatomic Potentials of He_{2}, Ne_{2}, Ar_{2}, and H_{2} by Wave Function Imaging.

We report on a direct method to measure the interatomic potential energy curve of diatomic systems. A cold target recoil ion momentum spectroscopy reaction microscope was used to measure the squares of the vibrational wave functions of H_{2}, He_{2}, Ne_{2}, and Ar_{2}. The Schrödinger equation relates the curvature of the wave function to the potential V(R) and therefore offers a simple but elegant way to extract the shape of the potential.

Spin and Angular Momentum in Strong-Field Ionization.

The spin polarization of electrons from multiphoton ionization of Xe by 395 nm circularly polarized laser pulses at 6×10^{13} W/cm^{2} has been measured. At this photon energy of 3.14 eV the above-threshold ionization peaks connected to Xe^{+} ions in the ground state (J=3/2, ionization potential I_{p}=12.1 eV) and the first excited state (J=1/2, I_{p}=13.4 eV) are clearly separated in the electron energy distribution. These two combs of above-threshold ionization peaks show opposite spin polarizations. The magnitude of the spin polarization is a factor of 2 higher for the J=1/2 than for the J=3/2 final ionic state. In turn, the data show that the ionization probability is strongly dependent on the sign of the magnetic quantum number.

Breakdown of the Spectator Concept in Low-Electron-Energy Resonant Decay Processes.

We suggest that low-energy electrons, released by resonant decay processes, experience substantial scattering on the electron density of excited electrons, which remain a spectator during the decay. As a result, the angular emission distribution is altered significantly. This effect is expected to be a common feature of low-energy secondary electron emission. In this Letter, we exemplify our idea by examining the spectator resonant interatomic Coulombic decay of Ne dimers. Our theoretical predictions are confirmed by a corresponding coincidence experiment.

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.

Erratum: Electron Localization in Dissociating H_{2}

This corrects the article DOI: 10.1103/PhysRevLett.116.043001.

Delocalization of a Vacancy across Two Neon Atoms Bound by the van der Waals Force.

We experimentally study 2p photoionization of neon dimers (Ne_{2}) at a photon energy of hν=36.56 eV. By postselection of ionization events which lead to a dissociation into Ne^{+}+Ne we obtain the photoelectron angular emission distribution in the molecular frame. This distribution is symmetric with respect to the direction of the charged vs neutral fragment. It shows an inverted Cohen-Fano double slit interference pattern of two spherical waves emitted coherently but with opposite phases from the two atoms of the dimer.