Ultrafast temporal evolution of interatomic Coulombic decay in NeKr dimers.

We investigate interatomic Coulombic decay in NeKr dimers after neon inner-valence photoionization [Ne+(2s-1)] using a synchrotron light source. We measure with high energy resolution the two singly charged ions of the Coulomb-exploding dimer dication and the photoelectron in coincidence. By carefully tracing the post-collision interaction between the photoelectron and the emitted ICD electron we are able to probe the temporal evolution of the state as it decays. Although the ionizing light pulses are 80 picoseconds long, we determine the lifetime of the intermediate dimer cation state and visualize the contraction of the nuclear structure on the femtosecond time scale.

Resonance signatures in the body-frame valence photoionization of CF4.

We present a combined experimental and theoretical investigation of the electron dynamics and body-frame angular dependence of valence photo-single ionization of CF4 and subsequent dissociation into CF3+ and F. Ionization from a valence t2 orbital shows overlapping shape resonances close to threshold that couple to the same total symmetry, leading to striking changes in the photoelectron angular distributions when viewed in the body-frame.

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.

Ejection of quasi-free-electron pairs from the helium-atom ground state by single-photon absorption.

We investigate the single-photon double ionization of helium at photon energies of 440 and 800 eV. We observe doubly charged ions with close to zero momentum corresponding to electrons emitted back to back with equal energy. These slow ions are the unique fingerprint of an elusive quasifree photon double ionization mechanism predicted by Amusia et al. nearly four decades ago [J. Phys. B 8, 1248 (1975)]. It results from the nondipole part of the electromagnetic interaction. Our experimental data are supported by calculations performed using the convergent close-coupling and time-dependent close-coupling methods.

Momentum-imaging apparatus for the study of dissociative electron attachment dynamics.

An ion-momentum spectrometer is used to study the dissociative dynamics of electron attachment to molecules. A skimmed, supersonic gas jet is crossed with a pulsed beam of low-energy electrons, and the resulting negative ions are extracted toward a time- and position-sensitive detector. Calculations of the momentum in three dimensions may be used to determine the angular dependence of dissociative attachment as well as the energetics of the reaction.

Imaging polyatomic molecules in three dimensions using molecular frame photoelectron angular distributions.

We demonstrate a method for determining the full three-dimensional molecular-frame photoelectron angular distribution in polyatomic molecules using methane as a prototype. Simultaneous double Auger decay and subsequent dissociation allow measurement of the initial momentum vectors of the ionic fragments and the photoelectron in coincidence, allowing full orientation by observing a three-ion decay pathway, (H+, H+, CH2(+)). We find the striking result that at low photoelectron energies the molecule is effectively imaged by the focusing of photoelectrons along bond directions.

Angular correlation between photoelectrons and auger electrons from K-shell ionization of neon.

We have used cold target recoil ion momentum spectroscopy to study the continuum correlation between the photoelectron of core-photoionized neon and the subsequent Auger electron. We observe a strong angular correlation between the two electrons. Classical trajectory Monte Carlo calculations agree quite well with the photoelectron energy distribution that is shifted due to the potential change associated with Auger decay. However, a striking discrepancy results in the distribution of the relative angle between Auger and photoelectron. The classical model predicts a shift in photoelectron flux away from the Auger emission direction, and the data strikingly reveal that the flux is lost rather than diverted, indicating that the two-step interpretation of photoionization followed by Auger emission is insufficient to fully describe the core-photoionization process.

Interference in the collective electron momentum in double photoionization of H2.

We investigate single-photon double ionization of H(2) by 130 to 240 eV circularly polarized photons. We find a double slitlike interference pattern in the sum momentum of both electrons in the molecular frame which survives integration over all other degrees of freedom. The difference momentum and the individual electron momentum distributions do not show such a robust interference pattern. We show that this interference results from a non-Heitler-London fraction of the H(2) ground state where both electrons are at the same atomic center.

Ultrafast probing of core hole localization in N2.

Although valence electrons are clearly delocalized in molecular bonding frameworks, chemists and physicists have long debated the question of whether the core vacancy created in a homonuclear diatomic molecule by absorption of a single x-ray photon is localized on one atom or delocalized over both. We have been able to clarify this question with an experiment that uses Auger electron angular emission patterns from molecular nitrogen after inner-shell ionization as an ultrafast probe of hole localization. The experiment, along with the accompanying theory, shows that observation of symmetry breaking (localization) or preservation (delocalization) depends on how the quantum entangled Bell state created by Auger decay is detected by the measurement.

The simplest double slit: interference and entanglement in double photoionization of H2.

The wave nature of particles is rarely observed, in part because of their very short de Broglie wavelengths in most situations. However, even with wavelengths close to the size of their surroundings, the particles couple to their environment (for example, by gravity, Coulomb interaction, or thermal radiation). These couplings shift the wave phases, often in an uncontrolled way, and the resulting decoherence, or loss of phase integrity, is thought to be a main cause of the transition from quantum to classical behavior. How much interaction is needed to induce this transition? Here we show that a photoelectron and two protons form a minimum particle/slit system and that a single additional electron constitutes a minimum environment. Interference fringes observed in the angular distribution of a single electron are lost through its Coulomb interaction with a second electron, though the correlated momenta of the entangled electron pair continue to exhibit quantum interference.

Single photon-induced symmetry breaking of H2 dissociation.

H2, the smallest and most abundant molecule in the universe, has a perfectly symmetric ground state. What does it take to break this symmetry? We found that the inversion symmetry can be broken by absorption of a linearly polarized photon, which itself has inversion symmetry. In particular, the emission of a photoelectron with subsequent dissociation of the remaining H+2 fragment shows no symmetry with respect to the ionic H+ and neutral H atomic fragments. This lack of symmetry results from the entanglement between symmetric and antisymmetric H+2 states that is caused by autoionization. The mechanisms behind this symmetry breaking are general for all molecules.

Electron correlation in the formation of hollow states along the Li-like isoelectronic sequence.

Hollow-state (double K-shell vacancy) production in Li-like Be+, B2+, C3+, and F6+ ions colliding with He has been investigated using high-resolution Auger-electron spectroscopy. The formation of discrete states and their relative intensities show striking dependences on the nuclear charge Z of the ion. From the projectile velocity dependences of these states the contribution of the electron-electron interaction is determined, showing that the hollow states are formed largely by electron correlation with a strength that diminishes for increasing Z.

Fully differential cross sections for photo-double-ionization of D2.

We report the first kinematically complete study of the four-body fragmentation of the D2 molecule following absorption of a single photon. For equal energy sharing of the two electrons and a photon energy of 75.5 eV, we observed the relaxation of one of the selection rules valid for He photo-double-ionization and a strong dependence of the electron angular distribution on the orientation of the molecular axis. This effect is reproduced by a model in which a pair of photoionization amplitudes is introduced for the light polarization parallel and perpendicular to the molecular axis.

Evidence for Pauli exchange leading to excited-state enhancement in electron transfer.

Single- and double-electron transfer to autoionizing 1s2l2l(') configurations in fluorine ions have been investigated for 1.1 MeV/u collisions of F7+ and F8+ with He and Ne. The resulting Auger electron emission spectra show anomolously large intensities for the formation of the metastable 1s(2s2p 3P) 4P state compared to the similarly configured 1s(2s2p 3P) 2P- and 1s(2s2p 1P) 2P+ states. The large 4P intensity, which cannot be explained on the basis of spin statistics, is attributed instead to the Pauli exchange of similarly aligned electrons.

Mechanisms of photo double ionization of helium by 530 eV photons.

We have measured fully differential cross sections for photo double ionization of helium 450 eV above the threshold. We have found an extremely asymmetric energy sharing between the photoelectrons and an angular asymmetry parameter beta approximately 2 and beta approximately 0 for the fast and slow electrons, respectively. The electron angular distributions show a dominance of the shakeoff for 2 eV electrons and clear evidence of an inelastic electron-electron scattering at an electron energy of 30 eV. The data are in excellent agreement with convergent close-coupling calculations.

Circular dichroism in K-shell ionization from fixed-in-space CO and N2 molecules.

We have measured the angular distributions of 1s photoelectrons excited by circularly and linearly polarized light from fixed-in-space CO and N2 molecules, in the vicinity of their shape resonances. A strong circular dichroism, i.e., a strong dependence on the sense of rotation of the polarization vector of the photons, is found for both molecules. State-of-the-art one-electron multiple scattering and partially correlated random phase approximation calculations are in good agreement with many, but not all, aspects of the experimental data.