Experimental Realization of Auger Decay in the Field of a Positive Elementary Charge.

Auger electron spectroscopy is an omnipresent experimental tool in many fields of fundamental research and applied science. The determination of the kinetic energies of the Auger electrons yields information about the element emitting the electron and its chemical environment at the time of emission. Here, we present an experimental approach to determine Auger spectra for emitter sites in the vicinity of a positive elementary charge based on electron-electron-electron and electron-electron-photon coincidence spectroscopy.

First (e,e) coincidence measurements on solvated sodium benzoate in water using a magnetic bottle time-of-flight spectrometer.

Understanding the mechanisms of X-ray radiation damage in biological systems is of prime interest in medicine (radioprotection, X-ray therapy…). Study of low-energy rays, such as soft-X rays and light ions, points to attribute their lethal effect to clusters of energy deposition by low-energy electrons. The first step, at the atomic or molecular level, is often the ionization of inner-shell electrons followed by Auger decay in an aqueous environment.

A modified magnetic bottle electron spectrometer for the detection of multiply charged ions in coincidence with all correlated electrons: decay pathways to Xe above xenon-4d ionization threshold.

Single-photon multiple photoionization results from electron correlations that make this process possible beyond the independent electron approximation. To study this phenomenon experimentally, the detection in coincidence of all emitted electrons is the most direct approach. It provides the relative contribution of all possible multiple ionization processes, the energy distribution between electrons that can reveal simultaneous or sequential mechanisms, and, if possible, the angular correlations between electrons.

Specific chemical bond relaxation unraveled by analysis of shake-up satellites in the oxygen single site double core hole spectrum of CO.

We recently developed [A. Ferté, , , 2020, , 4359] a method to compute single site double core hole (ssDCH or K) spectra. We refer to that method as NOTA+CIPSI.

Advanced Computation Method for Double Core Hole Spectra: Insight into the Nature of Intense Shake-up Satellites.

Double core hole spectroscopy is an ideal framework for investigating photoionization shake-up satellites. Their important intensity in a single site double core hole (ssDCH) spectrum allows the exploration of the subtle mix of relaxation and correlation effects associated with the inherent multielectronic character of the shake-up process. We present a high-accuracy computation method for single photon double core-shell photoelectron spectra that combines a selected configuration interaction procedure with the use of non-orthogonal molecular orbitals to obtain unbiased binding energy and intensity.

Multiple Auger decays of core-excited states in N.

Multi-electron coincidence measurements have been performed at the photon energies for the core-to-valence (1s → π) and core-to-Rydberg (1s → 3sσ and 3pπ) resonant excitations in N in order to investigate the dynamics of multiple Auger-electron emissions from these core-excited states in detail. Peaks due to slow electrons from superexcited atomic fragments are observed in the decay processes by emission of two or three Auger electrons, indicating stepwise (cascade) multiple Auger decays that involve faster dissociations than electronic relaxations. Energy partitions between the emitted electrons enable us to reveal the detailed decay mechanisms for these processes.

Double-core ionization photoelectron spectroscopy of CH: Breakdown of the "intuitive" ortho-meta-para binding energy ordering of KK states.

Single-site Double-Core Hole (ss-DCH or K) and two-site Double-Core Hole (ts-DCH or KK) photoelectron spectra including satellite lines were experimentally recorded for the aromatic CH molecule using the synchrotron radiation and multielectron coincidence technique. Density functional theory and post-Hartree-Fock simulations providing binding energies and relative intensities allow us to clearly assign the main K line and its satellites. KK states' positions and assignments are further identified using a core-equivalent model.

Photo-ionization and fragmentation of ScN@C following excitation above the Sc K-edge.

We have investigated the ionization and fragmentation of a metallo-endohedral fullerene, ScN@C, using ultrashort (10 fs) x-ray pulses. Following selective ionization of a Sc (1s) electron (hν = 4.55 keV), an Auger cascade leads predominantly to either a vibrationally cold multiply charged parent molecule or multifragmentation of the carbon cage following a phase transition.

Evidence of Extreme Ultraviolet Superfluorescence in Xenon.

We present a comprehensive experimental and theoretical study on superfluorescence in the extreme ultraviolet wavelength regime. Focusing a free-electron laser pulse in a cell filled with Xe gas, the medium is quasi-instantaneously population inverted by 4d-shell ionization on the giant resonance followed by Auger decay. On the timescale of ∼10  ps to ∼100  ps (depending on parameters) a macroscopic polarization builds up in the medium, resulting in superfluorescent emission of several Xe lines in the forward direction.

Cationic double K-hole pre-edge states of CS and SF.

Recent advances in X-ray instrumentation have made it possible to measure the spectra of an essentially unexplored class of electronic states associated with double inner-shell vacancies. Using the technique of single electron spectroscopy, spectra of states in CS and SF with a double hole in the K-shell and one electron exited to a normally unoccupied orbital have been obtained. The spectra are interpreted with the aid of a high-level theoretical model giving excellent agreement with the experiment.

Double-Core-Hole States in Neon: Lifetime, Post-Collision Interaction, and Spectral Assignment.

Using synchrotron radiation and high-resolution electron spectroscopy, we have directly observed and identified specific photoelectrons from K^{-2}V states in neon corresponding to simultaneous 1s ionization and 1s→valence excitation. The natural lifetime broadening of the K^{-2}V states and the relative intensities of different types of shakeup channels have been determined experimentally and compared to ab initio calculations. Moreover, the high-energy Auger spectrum resulting from the decay of Ne^{2+}K^{-2} and Ne^{+}K^{-2}V states as well as from participator Auger decay from Ne^{+}K^{-1}L^{-1}V states, has been measured and assigned in detail utilizing the characteristic differences in lifetime broadenings of these core hole states.

Photoelectron Spectroscopy of Ions: Study of the Auger Decay of the 4d→nf (n=4,5) Resonances in Xe^{5+} Ion.

We have studied, for the first time by electron spectroscopy, the Auger decay of the 4d→nf (n=4,5) resonances in Xe^{5+} ion. By detecting in coincidence the Auger electrons with the resulting Xe^{6+} ions, we unravel the contribution of the different final ionic states to the total cross section measured by ion spectroscopy. A strong intensity of 5s5p satellite lines has been observed, up to 4 times stronger than the 5s^{2} main lines.

Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions.

The formalism developed in the companion Paper I is used here for the interpretation of spectra obtained recently on the nitrogen molecule. Double core-hole ionization K(-2) and core ionization-core excitation K(-2)V processes have been observed by coincidence electron spectroscopy after ionization by synchrotron radiation at different photon energies. Theoretical and experimental cross sections reported on an absolute scale are in satisfactory agreement.

Single photon simultaneous K-shell ionization and K-shell excitation. I. Theoretical model applied to the interpretation of experimental results on H2O.

We present in detail a theoretical model that provides absolute cross sections for simultaneous core-ionization core-excitation (K(-2)V) and compare its predictions with experimental results obtained on the water molecule after photoionization by synchrotron radiation. Two resonances of different symmetries are assigned in the main K(-2)V peak and comparable contributions from monopolar (direct shake-up) and dipolar (conjugate shake-up) core-valence excitations are identified. The main peak is observed with a much greater width than the total experimental resolution.

Double photoionization in ring molecules: search of the cooper pair formation.

We provide a final state selective experimental study on the direct double photoionization of the valence states of benzene and pyrrole. The experiment is carried out using a magnetic-bottle electron time-of-flight coincidence setup at the incident photon energy region of 25-120 eV. We discuss on the recently discovered phenomenon of so-called Cooper pair formation [R.

Near-edge x-ray absorption fine structures revealed in core ionization photoelectron spectroscopy.

Simultaneous core ionization and core excitation have been observed in the C(2)H(2n) (n=1, 2, 3) molecular series using synchrotron radiation and a magnetic bottle time-of-flight electron spectrometer. Rich satellite patterns corresponding to (K(-2)V) core excited states of the K(-1) molecular ions have been identified by detecting in coincidence the photoelectron with the two Auger electrons resulting from the double core hole relaxation. A theoretical model is proposed providing absolute photoionization cross sections and revealing clear signatures of direct (monopolar) and conjugate (dipolar near-edge x-ray absorption fine structure) shakeup lines of comparable magnitude.

Electron reemission processes following photoelectron recapture due to post-collision interaction in inner-shell photoionization of water molecules.

Electron reemission following photoelectron recapture due to post-collision interaction has been studied at 0.7 eV the inner-shell photoionization threshold of water molecules, using a multi-electron coincidence method. Electron reemissions after single Auger decay occur from O and OH fragments which are produced by the dissociations of high-n Rydberg H2O(+) states populated through photoelectron recapture.

Single photon K(-2) and K(-1)K(-1) double core ionization in C(2)H(2n) (n=1-3), CO, and N(2) as a potential new tool for chemical analysis.

We have observed single photon double K-shell photoionization in the C(2)H(2n) (n=1-3) hydrocarbon sequence and in N(2) and CO, using synchrotron radiation and electron coincidence spectroscopy. Our previous observations of the K(-2) process in these molecules are extended by the observations of a single photon double photoionization with one core hole created at each of the two neighboring atoms in the molecule (K(-1)K(-1) process). In the C(2)H(2n) sequence, the spectroscopy of K(-1)K(-1) states is much more sensitive to the bond length than conventional electron spectroscopy for chemical analysis spectroscopy based on single K-shell ionization.

Decay of a 2p inner-shell hole in an Ar(+) ion.

Direct measurements of the photoelectrons or Auger electrons associated with inner shell ionization of positively charged ions are extremely difficult and rarely realized. We propose an alternative method to simulate such measurements, based on core valence double photoionization of the neutral species. As an example, we obtain the spectroscopy, lifetimes, and Auger decays of the states arising from 2p inner shell ionisation of an Ar(+) ion.

A local chemical environment effect in site-specific Auger spectra of ethyl trifluoroacetate.

We have investigated a local chemical environment effect on Auger spectra of ethyl trifluoroacetate (C(4)H(5)F(3)O(2)), using multi-electron coincidence spectroscopy and high-resolution electron spectroscopy. Site-specific KVV Auger spectra for each carbon atom, and for the fluorine and oxygen atoms are presented. The extent of hole localization in the final dicationic states was investigated with the help of theoretical calculations based on a two-hole population analysis.

Auger decay of molecular double core-hole and its satellite states: comparison of experiment and calculation.

Auger decay of the C(2)H(2) double core-hole (DCH) states, including the single-site DCH (C1s(-2)), two-site DCH (C1s(-1)C1s(-1)), and satellite (C1s(-2)π(-1)π∗(+1)) states, has been investigated experimentally using synchrotron radiation combined with multi-electron coincidence method, and theoretically with the assumption of the two-step sequential model for Auger decay of the DCH states. The theoretical calculations can reproduce the experimental two-dimensional Auger spectra of the C(2)H(2) single-site DCH and satellite decays, and allow to assign the peaks appearing in the spectra in terms of sequential two-electron vacancy creations in the occupied valence orbitals. In case of the one-dimensional Auger spectrum of the C(2)H(2) two-site DCH decay, the experimental and calculated results agree well, but assignment of peaks is difficult because the first and second Auger components overlap each other.

Communication: Formation of slow electrons in the Auger decay of core-ionized water molecules.

Double Auger decay of O1s(-1) and its satellite states in H(2)O has been studied with a multi-electron coincidence method, and a process leading to autoionizing O* fragments has been revealed. The breaking of the two O-H bonds producing the autoionizing O* fragments occurs for highly excited H(2)O(2+) populated by the initial Auger decay. The O* fragments are more favorably produced in the decay from the satellite states, resulting from the larger population of highly excited H(2)O(2+) states inheriting the valence excitation in the initial state.

Evidence of single-photon two-site core double ionization of C2H2 molecules.

We observe the formation in a single-photon transition of two core holes, each at a different carbon atom of the C2H2 molecule. At a photon energy of 770.5 eV, the probability of this 2-site core double ionization amounts to 1.

Energy correlation among three photoelectrons emitted in core-valence-valence triple photoionization of Ne.

The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne3+ in the 1s 2s2 2p4 configuration is observed.

Triple ionization of CO2 by valence and inner shell photoionization.

Spectra of triply ionized CO(2) have been obtained from photoionization of the molecule using soft x-ray synchrotron light and an efficient multi-electron coincidence technique. Although all states of the CO(2) (+++) trication are unstable, the ionization energy for formation of molecular ions at a geometry similar to that of the neutral molecule is determined as 74 ± 0.5 eV.