Intramolecular electron scattering and electron transfer following autoionization in dissociating molecules

Resonant Auger decay of core-excited molecules during ultrafast dissociation leads to a Doppler shift of the emitted electrons depending on the direction of the electron emission relative to the dissociation axis. We have investigated this process by angle-resolved electron-fragment ion coincidence spectroscopy. Electron energy spectra for selected emission angles for the electron relative to the molecular axis reveal the occurrence of intermolecular electron scattering and electron transfer following the primary emission. These processes amount to approximately 25% of the resonant atomic Auger intensity emitted in the studied transition.     

Energy and angular distributions of electrons emitted by direct double auger decay

We have observed the direct L(2,3)MMM double Auger transition after photoionization of the 2p shell of argon by angle-resolved electron-electron coincidence spectroscopy. The process is responsible for about 20% of the observed Auger electron intensity. In contrast to the normal Auger lines, the spectra in double Auger decay show a continuous intensity distribution. The energy and angular distributions of the emitted electrons allow one to obtain information on the electron correlations giving rise to the double Auger process as well as the symmetry of the associated two-electron continuum state.     

Dynamics and post-collision interaction effects in two electron decay from the Xenon 4d hole

Two Auger electrons, one very slow, one fast, have been detected in coincidence following near threshold 4d photoionization of the Xe atom. The distribution in the energy the two electrons share has been measured for the first time revealing the presence of post-collision interaction effects that provide unique information on the decay dynamics of the 4d hole. Analysis of the distorted line shapes indicates that the dominant process is decay of Xe+(4d(-1)) to Xe3+ through cascade emission of a zero kinetic energy Auger electron followed by a fast Auger electron. The widths of the intermediate Xe2+* states are estimated to be about 60 meV.     

(e,2e) and (e,3-1e) coincidence experiments for studying the PCI effect of low energy ionizing electrons in the Auger process of Ar

Our (e,3-1e) measurements for studying the post-collision interaction (PCI) after electron impact inner shell ionization of argon were continued and completed at different energy conditions. Emitted LMM Auger electrons are detected in coincidence with the ionizing scattered electrons and the energy of the slow PCI inducer ejected electron was calculated from energy conservation. Particularly the effect of the very low energy (i.e. 0–5 eV) ejected electrons (strongly asymmetric energy sharing) is studied at 500 and 460 eV primary electron energies. In the latter case, the background caused by outer-shell electrons was measured by itself and then removed from the coincident spectrum. Nevertheless, the evaluation of PCI distorted Auger lines is still considerably disturbed by the resonant Auger electrons from the high Rydberg states, their (e,2e) contribution was estimated in the paper.     

Mechanisms of spontaneous two-electron emission from core-excited states of molecular CO

We demonstrate that the observation of slow electrons emitted in the decay of molecular core-excited states can be a sensitive probe of the double Auger processes, and that in combination with electron-electron coincidence spectroscopy, it can provide clear insight into the mechanisms involved. The present study identifies all cascade Auger paths from the C1s-to-Rydberg states in CO to final states of CO2+. One pathway includes the first directly identified case of molecular level-to-level autoionization of a cation and shows remarkable selectivity for a specific final state.     

Multielectron spectroscopy: the xenon 4d hole double auger decay

A magnetic bottle spectrometer of the type recently developed by Eland et al. [Phys. Rev. Lett. 90, 053003 (2003).] has been implemented for use with synchrotron radiation, allowing multidimensional electron spectroscopy. Its application to the Xe 4d double Auger decay reveals all the energy pathways involved. The dominant path is a cascade process with a rapid (6 fs) ejection of a first Auger electron followed by the slower (>23 fs) emission of a second Auger electron. Weaker processes implying 3 electron processes are also revealed, namely, direct double Auger and associated Rydberg series.     

Development of a new experimental setup for studying collisions of keV-electrons with thick and thin targets

Development of a new lectron-recoil ion/photon coincidence setup for investigating some of the electron induced collision processes, such as electron bremsstrahlung, electron backscattering, innershell excitation and multiple ionization of target atoms/molecules in bombardment of electrons having energies from 2.0 keV to 30.0 keV with solid and gaseous targets is described. The new features include the use of a compact multipurpose scattering chamber, a time-of-flight spectrometer for detection of multiply charged target ions, a 45°-parallel plate electrostatic analyzer for measuring energy and angle of the ejected electrons, a room temperature high resolution Si-PIN photo diode X-ray detector for counting the collisionally induced photons, a coincidence data acquisition system consisting of a 200 MHz Pentium based 8K-multichannel analyzer and a standard network of a fast/slow coincidence electronics. In particular, the details of design, fabrication and assembly of indigenous components employed in the setup are presented. Selected experiments planned with the setup are mentioned and briefly discussed. A report on performance, optimization, efficiency, time resolution etc. of the time-of-flight (TOF) spectrometer and that of the 45°-parallel plate electrostatic analyzer (PPEA) is presented. Test spectra of electron-recoil ion coincidences, energy distribution of ejected electrons and characteristic plus non-characteristic X-ray spectrum are illustrated to exhibit the satisfactory performance of the developed setup.     

Nuclear dissociation after the O 1s $\rightarrow (^4\Sigma_\text{u}^-)$3sσ excitation in O$_2$ molecules

We investigate the dissociation dynamics of core-excited $\mathrm{O}_2$ molecules using a high-resolution energy-resolved electron-ion coincidence experimental setup. The excited cationic states with two valence holes and one Rydberg electron are created after spectator Auger decay induced by $\mathrm{O}$ 1s $\rightarrow (^4\Sigma_{\rm u}^-)3{\rm s}\sigma$ core excitation in $\mathrm{O}_2$. From the energy correlation between the kinetic energy of the Auger electron and the ion kinetic energy release, we distinguish several dissociation channels. Rather complex dissociation channels of the spectator Auger final states are disclosed, which can be explained by the increased number of the crossing point due to the existence of Rydberg electron. The quantum system will evolve into different dissociation limits at each crossing point between the potential energy curves.     

Experimental evidence of interatomic coulombic decay from the auger final states in argon dimers

Interatomic Coulombic decay (ICD) from an Auger-final dicationic state is observed in the Ar dimer. A 2p inner-shell vacancy created by photoionization is replaced with 3s and 3p vacancies via intra-atomic Auger decay. The Auger-final dicationic state is subject to ICD in which one of the 3p electrons in the same Ar atom fills the 3s vacancy while one of the 3p electrons from the neighboring Ar atom is emitted as an ICD electron. This ICD process is unambiguously identified by electron-ion-ion coincidence spectroscopy in which the kinetic energy of the ICD electron and the kinetic energy release between Ar+ and Ar2+ are measured in coincidence.     

Many-electron effects in the Auger-photoelectron coincidence spectroscopy spectra of the late 3d-transition metals

The valence hole created by the L2–L3 M45 Coster–Kronig (CK) transition may hop away from the ionized atomic site before the L3-hole decays. Then when the third (Auger) electron emitted by the L3-hole decay is measured in coincidence with the photoelectron emitted by the initial L2-level electron ionization, the coincidence spectrum becomes similar or identical to the singles spectrum of the secondary (Auger) electron emitted by the L3-hole decay as if it decayed as an initial single core hole. Thus the coincidence spectrum is essentially governed by the valence-hole dynamics of both the intermediate states and the final states of the L2–L3 (M45) CK-transition preceded Auger transition. In the present paper the Auger-photoelectron coincidence spectroscopy (APECS) spectra of Fe, Co, and Ni metals reported by C.P. Lund et al. (Phys. Rev. B55 (1997) 5455) are analyzed in light of the delocalization and localization of the valence hole(s) created by the CK transition or the CK-transition preceded Auger transition.     

Unveiling residual molecular binding in triply charged hydrogen bromide

We present an experimental and theoretical study of triply charged hydrogen bromide ions formed by photoionization of the inner 3d shell of Br. The experimental results, obtained by detecting the 3d photoelectron in coincidence with the two subsequent Auger electrons, are analyzed using calculated potential energy curves of HBr3+. The competition between the short-range chemical binding potential and the Coulomb repulsion in the dissociative process is shown. Two different mechanisms are observed for double Auger decay: one, a direct process with simultaneous ejection of two Auger electrons to final HBr3+ ionic states and the other, a cascade process involving double Auger decay characterized by the autoionization of Br*+ ion subsequent to the HBr2+ fragmentation.     

Auger electron spectroscopy studies of CO on Ni spectral line shapes and quantitative aspects

The true secondary electron peak of aluminium is observed during the cleaning process controlled by Auger spectroscopy. The features which appear are studied in relation with the electron energy loss spectrum. This observation confirms the hypothesis of emission of secondary electrons by the plasmon decay.     

Effect of relaxation and decay of a charge transfer shakeup satellite on Auger-electron spectroscopy spectra and Auger-photoelectron coincidence spectroscopy spectra of adsorbates

An electron excited to an unoccupied part of adsorbate–substrate hybrid states in a chemisorbed molecule by a resonant core electron excitation or charge transfer (CT) shakeup may delocalize on time scale of core-hole decay so that the excited core-hole state relaxes partly or completely to a fully relaxed one. The Auger decay of the fully relaxed core-hole state via the relaxation of the excited one introduces an additional feature in the resonant Auger-electron spectroscopy (RAES) spectrum and the AES spectrum. However, the additional feature in the RAES spectrum is a normal AES spectrum by decay of the fully relaxed core-hole state, whereas the one in the AES spectrum is the AES spectrum by decay of the fully relaxed core-hole state broadened by the photoelectron spectroscopy (PES) CT shakeup satellite weighted by the branching ratio of the relaxation width. The discrepancies between the AES spectrum measured at high above the ionization threshold and the additional feature in the RAES spectrum consist of the symmetric-like part by the decay of the fully relaxed core-hole state via the relaxation of the CT shakeup state and the asymmetric part by the direct decay of the shakeup states. The asymmetric part increases with a decrease in the hybridization strength. This explains the variation with the hybridization strength in the discrepancies between the RAES spectra and the AES spectra of chemisorbed molecules such as CO/Ni, CO/Cu and CO/Ag. A comparison of the singles PES spectrum with the one measured in coincidence with the AES main line of a selected kinetic energy (KE) provides the delocalization rate of the excited electron in the CT shakeup state as a function of photoelectron KE. The coincidence measurement to obtain the partial singles PES spectrum is discussed.     

Use of electron correlation to make attosecond measurements without attosecond pulses

We describe how correlations between electrons can be used to trace the dynamics of correlated two-electron ionization with attosecond precision, without using attosecond pulses. The approach is illustrated using the example of Auger or Coster-Kronig decay triggered by photoionization with an extreme ultraviolet pulse. It requires correlated measurements of angle-resolved energy spectra of both the photo- and Auger electrons in the presence of a laser pulse. To reconstruct the dynamics, we use not only classical time and energy correlation, but also entanglement between the two electrons.     

Inelastic interactions of protons and electrons with biologically relevant molecules

Ionization and fragmentation of water and uracil molecules was studied both by electron and proton impact. A special coincidence technique allows on an event by event basis the investigation of product ions formed upon the collision of protons with neutral molecules including the identification of the charge state of the projectile. This enables the characterization of the ionization processes occurring, i.e. direct ionization, single electron capture or double electron capture for 0, 1 or 2 electrons that are transferred from the target to the projectile, respectively. For uracil the fragmentation patterns obtained by electron and proton impact ionization reveal close similarities and indicate a comparable amount of excitation for the two different ionization mechanisms at high enough projectile energies. Received 25 February 2002 Published online 13 September 2002     

Femtosecond energy relaxation in suspended graphene: phonon-assisted spreading of quasiparticle distribution

Ultra-fast optical measurements of few-layer suspended graphene films grown by chemical vapor deposition were performed with femtosecond pump–probe spectroscopy. The relaxation processes were monitored in transient differential transmission (ΔT/T) after excitation at two different wavelengths of 350 and 680 nm. Intraband electron–electron scattering, electron–phonon scattering, interband Auger recombination and impact ionization were considered to contribute to ΔT/T. All these processes may play important roles in spreading the quasiparticle distribution in time scales up to 100 fs. Optical phonon emission and absorption by highly excited non-equilibrium electrons were identified from ΔT/T peaks in the wide spectral range. When the probe energy region was far from the pump energy, the energy dependence of the quasiparticle decay rate was found to be linear. Longer lifetimes were observed when the quasiparticle population was localized due to optical phonon emission or absorption.     

Auger electron emission from fixed-in-space CO

We have measured the angular distribution of carbon K-Auger electrons from fixed in space, core-ionized, CO molecules in coincidence with the kinetic energy release of the C+ and O+ fragments. We find a very narrow ejection of Auger electrons in the direction of the oxygen and an oscillatory diffraction pattern. Even for similar electron energies, the angular distribution strongly depends on the symmetry of the final state.     

Design of an Auger Electron Mössbauer Spectrometer (AEMS) using a modified cylindrical mirror analyzer

We have designed and built an Auger Electron Mössbauer Spectrometer (AEMS) for the detection of resonant ⁵⁷Fe Auger electrons using a modified commercial cylindrical mirror analyzer (CMA). The CMA final aperture was modified intentionally in order to increase electron transmission at the expense of reducing its energy resolution, from an original value of 0.5 % to a value of 11 % after the modification. The Channeltron detector electronics and the pre-amplifier were also modified in order to increase the counting efficiency. The electron energy analyzer is selective in energy in the 30 eV–3000 eV range, so the spectrometer can be used to detect MNN (45 eV) and LMM (600–700 eV) Fe Auger signals, what gives it a high surface sensitivity for Fe containing samples. We have used it to acquire the Fe LMM Auger signals generated from the de-excitation process after γ-Ray resonant nuclear absorption. The spectrometer can be used to study samples non-enriched in ⁵⁷Fe, with acquisition times from 5 to 7 days, what is a big advantage. From electron trajectory Monte Carlo simulations in metallic iron, the mean-escape-depth of the detected Auger signals has been estimated in approximately 1 nm. Fe K conversion electrons and KLL Auger electrons with mean escape depths of 129 nm and 78 nm respectively also contribute to the detected signal although in a lesser proportion.     

The fragmentation of CCl4 dications studied by Auger electron-ion coincidence experiments

The formation and decay of dication states of tetrachloromethane has been studied in an electron impact experiment by Auger electron-ion coincidence measurements. The fragmentation following the Cl2p ionization has been studied in three different binding energy regions of the dication between 33.5 and 48.5 eV. In the experimental data no bound stable or metastable CCl₄²⁺ states have been observed and the fragmentation pattern of the dications resulted to be strongly dependent on the state and geometry of the dication.