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Single-site Double-Core Hole (ss-DCH or K -2 ) and two-site Double-Core Hole (ts-DCH or K -1 K -1 ) photoelectron spectra including satellite lines were experimentally recorded for the aromatic C 6 H 6 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 -2 line and its satellites. K -1 K -1 states' positions and assignments are further identified using a core-equivalent model. We predict that, contrary to what has been observed in the C 2 H 2n series of molecules, the K -1 K -1 energy-level ordering in C 6 H 6 does not reflect the core-hole distances between the two holes.

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. This broadening is the signature of nuclear dynamics.

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. The evolution with photon energy of the relative contribution of shake-up and conjugate shake-up processes is discussed. The first main resonance in the K(-2)V spectrum is assigned to a K(-2)π(∗) state mainly populated by the 1s→ lowest unoccupied molecular orbital dipolar excitation, as it is in the K(-1)V NEXAFS (Near-Edge X-ray Absorption Fine Structure) signals. Closer to the K(-2) threshold Rydberg resonances have been also identified, and among them a K(-2)σ(∗) resonance characterized by a large amount of 2s/2p hybridization, and double K(-2)(2σ(∗)/1π/3σ)(-1)1π(∗2) shake-up states. These resonances correspond in NEXAFS spectra to, respectively, the well-known σ(∗) shape resonance and double excitation K(-1)(2σ(∗)/1π/3σ)(-1)1π(∗2) resonances, all being positioned above the threshold.

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. The Auger spectra have been simulated using a statistical approach. It is found that all Auger decays populate mainly localized dicationic states, with the two holes located either on the same fluorine atom or on adjacent fluorine atoms. While the decay of the F 1s hole populates exclusively the former states, the latter class of states is also populated by the decay of the C and O 1s holes.

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. The theoretical calculations on the Auger decay of the N(2) single-site DCH state, approximately considering the effect of nuclear motion, suggest that the nuclear motion, together with the highly repulsive potential energy curves of the final states, makes an important effect on the energy distribution of the Auger electrons emitted in the second Auger decay.

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., (© 2011 American Institute of Physics)

Spectra of triply charged carbon disulphide have been obtained by measuring, in coincidence, all three electrons ejected in its formation by photoionization. Measurements of the CS(2)(3+) ion in coincidence with the three electrons identify the energy range where stable trications are formed. A sharp peak in this energy range is identified as the (2)Pi ground state at 53.1+/-0.1 eV, which is the lowest electronic state according to ab initio molecular orbital calculations. Triple ionization by the double Auger effect is provisionally divided, on the basis of the pattern of energy sharing between the two Auger electrons into contributions from direct and cascade Auger processes. The spectra from the direct double Auger effect via S 2p, S 2s, and C 1s hole states contain several resolved features and show selectivity based on the initial charge localization and on the identity of the initial state. Triple ionization spectra from single Auger decay of S 2p-based core-valence states CS(2)(2+) show retention of the valence holes in this Auger process. Related ion-electron coincidence measurements give the triple ionization yields and the breakdown patterns in triple photoionization at selected photon energies from 90 eV to above the inner shell edges.

We investigate the use of complex absorbing potentials for the calculation of partial cross sections in multichannel photofragmentation processes. An exactly solvable, coupled-two-channel problem involving square-well potentials is used to compare the performance of various types of absorbing potentials. Special emphasis is given to the near-threshold regions and the conditions under which the numerical results are able to reproduce the Wigner threshold laws. It was found that singular, transmission-free absorbing potentials perform better than those of power or polynomial form.

We combine the Lanczos algorithm with the absorbing-potential method, implemented in a discrete variable representation to calculate the near-threshold photodissociation cross sections of CH+. The method is iterative, based on a continued fraction representation of the Green function and avoids any explicit matrix diagonalization. A very good agreement is found with experiment and close-coupling calculations., ((c) 2005 American Institute of Physics.)