RESUMEN
The dynamics of the photofragmentation pathways of tetrachloroethylene with photon energies from 15 up to 250 eV encompassing the Cl 2p edge is presented. In order to distinguish the fragmentation channels, the ionic fragments were separated according to their mass-to-charge ratio, measured in coincidence with the photoelectrons, and collected as a function of the incident photon energy. Distinct minima or maxima are found in the partial ion yield in the region between 40 and 50 eV. These features are believed to be associated with the Cooper minimum which results from a molecular orbital with a strong atomic 3p subshell character. In the shallow core region, some fragmentation patterns are considered in terms of fast fragmentation of the C2Cl4 molecule, despite the heavy mass of its fragments. In the present case, the fast fragmentation is favored by the very strong antibonding character of the LUMO, understandable in the frame of the core equivalent model for halogen-containing molecules. In addition, ab initio calculations were performed to obtain states at the Cl 2p edge. Singlet and triplet states at the Cl 2p edge of the C2Cl4 molecule, corresponding to the Cl(2p â 9b1u*) and Cl(2p â 8b2u*) transitions, were calculated in order to form a basis set of molecular states from which the spin-orbit splitting can be inferred. Multiconfigurational self-consistent field (MCSCF) calculation followed by multireference configuration interaction (MRCI) was the method chosen to establish a set of singlet and triplet states at the 2p excitation edge in addition to the ground state.
RESUMEN
We report the discovery of the formation of an electron Cooper pair approximately 40 eV above the double-ionization threshold in benzene, naphthalene, anthracene, and coronene after absorption of a single photon. We have measured the ratios of doubly to singly charged parent ions of the above mentioned molecules as well as pyrrole and furan by using monochromatized synchrotron radiation up to 100 eV above the corresponding thresholds. We also recorded photoelectron spectra of benzene and naphthalene at selected energies. The electron-pair formation is based on the specific structure of the molecules and does not exist for pyrrole and furan.
RESUMEN
We have measured the ratio of doubly to singly charged parent ions of benzene, naphthalene, anthracene, and pentacene using monochromatized synchrotron radiation up to 30 eV above the corresponding threshold. Our measurements show a striking similarity between the ratio of doubly charged to all parent ions and the ratio for helium. Moreover, the magnitudes of the ratios for these molecules scale linearly with their lengths with an amazing accuracy. A high ratio, i.e., a high relative double-photoionization probability, makes a molecule an important source of low-energy electrons that can promote radiation damage of biomolecules [B. Boudaïffa et al., Science 287, 1658 (2000)].
RESUMEN
Observations are reported for the first time of significant nondipole effects in the photoionization of the outer-valence orbitals of diatomic molecules. Measured nondipole angular-distribution parameters for the 3sigma(g), 1pi(u), and 2sigma(u) shells of N2 exhibit spectral variations with incident photon energies from thresholds to approximately 200 eV which are attributed via concomitant calculations to particular final-state symmetry waves arising from (E1)multiply sign in circle(M1,E2) radiation-matter interactions first-order in photon momentum. Comparisons with previously reported K-edge studies in N2 verify linear scaling with photon momentum, accounting in part for the significantly enhanced nondipole behavior observed in inner-shell ionization at correspondingly higher momentum values in this molecule.
RESUMEN
The relative double-photoionization cross section of neutral C60 clusters was investigated using monochromatized synchrotron radiation between 18 and 283 eV. Our measurement of the double-to-single photoionization ratio reveals two modulating components that are superimposed on a smooth ratio curve from threshold (19.0 eV) up to 280 eV, when inner-shell excitations become possible. The maxima in the modulation can be related to geometrical dimensions of the C60 cluster.
RESUMEN
The threshold region of the double-photoionization cross section of atomic beryllium was investigated using monochromatized synchrotron radiation. The photon energy dependence of the double-photoionization cross section can be described by the Wannier power law up to 1.7 eV above threshold. However, we unexpectedly find oscillations in the cross section, which are in excellent agreement with a modulated threshold law based on the Coulomb-dipole theory [Phys. Rev. Lett. 49, 365 (1982)]]. This new finding casts some doubts on the general applicability of the Wannier power law.
RESUMEN
The Xe 5s nondipole photoelectron parameter gamma is obtained experimentally and theoretically from threshold to approximately 200 eV photon energy. Significant nondipole effects are seen even in the threshold region of this valence shell photoionization. In addition, contrary to previous understanding, clear evidence of interchannel coupling among quadrupole photoionization channels is found.
RESUMEN
The threshold region of the double-photoionization cross section of lithium was investigated using monochromatized synchrotron radiation and ion time-of-flight spectrometry. While the overall energy dependence can be described by the Wannier power law, we found oscillations in the cross section which are in good agreement with a modulated threshold law as proposed by Temkin [Phys. Rev. Lett. 49, 365 (1982)]]. This behavior may be due to the unequal binding energies of the electrons involved in the double-photoionization process.
RESUMEN
We have observed photoexcitation of the dipole-forbidden 1s(2) 1S0-->2p(2) 1D2 resonance in helium by measuring the nondipolar forward-backward asymmetry of photoelectron angular distributions in the 2l2l(') autoionizing region. By exploiting the electric dipole-quadrupole interference in the excitation of both the 2s2p 1P1 and 2p(2) 1D2 levels, we have observed the quadrupole resonance in photoabsorption and extracted its Fano line shape parameters and the relative phase of the 1sEp and 1sEd continua. We find the quadrupole line profile index q(2) to be markedly different from theoretical expectations.
RESUMEN
Second-order [ O(k(2)), k = omega/c] nondipole effects in soft-x-ray photoemission are demonstrated via an experimental and a theoretical study of angular distributions of neon valence photoelectrons in the 100-1200 eV photon-energy range. A newly derived theoretical expression for nondipolar angular distributions characterizes the second-order effects using four new parameters with primary contributions from pure-quadrupole and octupole-dipole interference terms. Independent-particle calculations of these parameters account for a significant portion of the existing discrepancy between experiment and theory for Ne 2p first-order nondipole parameters.
