Oliver Hemmers

High-resolution electron time-of-flight apparatus for the soft x-ray region

A gas-phase time-of-flight (TOF) apparatus, capable of supporting as many as six electron-TOF analyzers viewing the same interaction region, has been developed to measure energy- and angle-resolved electrons with kinetic energies up to 5 keV. Each analyzer includes a newly designed lens system that can retard electrons to about 2% of their initial kinetic energy without significant loss of transmission; the analyzers can thus achieve a resolving power (E/ΔE) greater than 104 over a wide kinetic-energy range. Such high resolving power is comparable to the photon energy resolution of state-of-the-art synchrotron–radiation beamlines in the soft x-ray range, opening the TOF technique to numerous high-resolution applications. In addition, the angular placement of the analyzers, by design, permits detailed studies of nondipolar angular distribution effects in gas-phase photoemission.

Electric-octupole and pure-electric-quadrupole effects in soft-X-Ray photoemission

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.

THE K-SHELL AUGER DECAY OF ATOMIC OXYGEN

Relative photoionization cross sections for and produced by the Auger decay of a 1s hole in atomic oxygen were measured by using synchrotron radiation between 525 and 553 eV. Energies and quantum defects of the members of the two Rydberg series converging to and ionization thresholds were determined. In addition, the and ionization thresholds were calculated from the two Rydberg series. The 182 meV resolution of the monochromator allowed a detailed study over both thresholds revealing evidence for post-collision interaction and allowing a comparison of the ionization continuum above both and thresholds with that of the ionization continuum above the Ar edges. This comparison indicates that the lifetimes of the Ar(2p) and O(1s) hole states are approximately the same.

Beyond the dipole approximation: angular-distribution effects in valence photoemission

Angular distributions of valence photoelectrons showing effects due to higher-multipole photon interactions have been measured for the first time. Neon 2s and 2p photoemission exhibits effects beyond the dipole approximation throughout the 250 - 1200 eV photon-energy range studied. The results suggest that any photoemission experiment, on any sample, can be affected at relatively low photon energies, pointing to a general need for caution in interpreting angle-resolved-photoemission measurements.

Breakdown of the dipole approximation in soft-X-ray photoemission

Abstract Although breakdowns in the dipole approximation in the soft-X-ray photon-energy range ( h ν≤5 keV) were first observed 30 years ago and have been studied theoretically for many years, their significance at low energies has remained generally unappreciated within the broader photoemission community. Advances in gas-phase photoemission experiments using synchrotron radiation have recently highlighted nondipole effects at relatively low energies while probing the limits of the dipole approximation. Breakdowns in this approximation are manifested primarily as deviations from dipolar angular distributions of photoelectrons. Detailed new results demonstrate nondipolar angular-distribution effects are easily observable in atomic gases at energies well below 1 keV, and, in molecules, a previously unexpected phenomenon greatly enhances the breakdown of the dipole approximation just above core-level ionization thresholds. A progress report on this newly burgeoning area from an experimental perspective is presented here, including a brief history, a description of recent advances, graphical representations of nondipolar angular distributions, a re-evaluation of the classic first experiment in the soft-X-ray range and a look to the future.

Fragmentation of methyl chloride studied by partial positive and negative ion-yield spectroscopy

The authors present partial-ion-yield experiments on the methyl chloride molecule excited in the vicinity of the Cl2p and C1s inner shells. A large number of fragments, cations produced by dissociation or recombination processes, as well as anionic species, have been detected. Although the spectra exhibit different intensity distributions depending on the core-excited atom, general observations include strong site-selective fragmentation along the C-Cl bond axis and a strong intensity dependence of transitions involving Rydberg series on fragment size.

On the angular distributions of electrons photoejected from fixed-in-space and randomly oriented molecules

Abstract New theoretical expressions are devised from a dynamical perspective for molecular photoionization cross sections differential in electron ejection angles which facilitate comparisons between theory and experiment and provide a convenient basis for ab initio calculations. The cross sections obtained for fixed-in-space molecules, including the lowest-order (nondipole) effects of retardation, are given in terms of invariant molecular body-frame transition moments and related normalized angular-distribution amplitudes which can be calculated employing interaction-prepared states without reference to specific scattering boundary conditions. Corresponding expressions for molecular dipole and nondipole anisotropy factors appropriate for randomly oriented molecules are obtained in closed forms involving expectation values of harmonic polynomials over the fixed-in-space body-frame angular-distribution amplitudes. The expressions are seen to be in the spirit of corresponding results for atomic photoionization anisotropy factors, to which they reduce in appropriate limits. Interpretations of recently measured angular distributions of photoelectrons from the K-shell of molecular nitrogen illustrate how the development relates measurements on randomly oriented molecules to those performed on fixed-in-space molecules. The theoretical formalism provides results in excellent accord with measurements of the molecular nitrogen K-shell dipole anisotropy factor, and accounts for the origins of large nondipole effects observed at relatively low photon energies (ℏω≤500 eV) in the measured angular distributions.

Photon energy dependence of ionization-excitation in helium at medium energies

We have measured the photoionization-excitation-to-photoionization ratio for (n = 2 - 6) at several photon energies from 90 to 900 eV. By extrapolating these values we could determine the asymptotic high-energy ratios for (n = 2 - 5) which agree with theoretical predictions. We show that the satellite-to-main-line ratios are consistent with experimental double-to-single photoionization ratios and agree well with recent measurements.

Anion formation moderated by post-collision interaction following core-level photoexcitation of CO

The photon-energy dependence of the oxygen-anion (O−) yield has been measured following photoexcitation of CO just above both the C and O K-shell ionization thresholds. The observed exponentially decaying yields above both edges are attributed to a post-collision interaction (PCI) between the emitted photoelectron and the CO molecule. Using a modified semi-classical atomic model, the near-threshold spectra can be reproduced if an energy shift is included. The shift in photon energy above the C K edge is greater than above the O K edge. The difference is attributed to a site-dependent PCI effect related to the polarity of the valence orbitals of the CO molecule.

Photofragmentation of third-row hydrides following photoexcitation at deep-core levels

The relaxation dynamics of HCl, DCl, H2S, and D2S following photoexcitation in the vicinities of the Cl and S K-shell thresholds ( ;2.8 keV for Cl, ;2.5 keV for S! were studied by means of ion time-of-flight mass spectroscopy. In all cases, the onset of pre-edge core-shell photoionization precedes the formation on resonance of a significant amount of neutral hydrogen as well as postcollision-interaction effects above threshold. Examination of the width of the H 1 peak in spectra taken with the analyzer parallel and perpendicular to the polarization vector of the incident light indicates that on resonance, the photofragmentation asymmetry parameter, b, is approximately two for HCl, and is clearly positive for H2S. @S1050-2947~98!08211-0# PACS number~s!: 33.80.Gj, 33.80.Eh Time-of-flight mass spectroscopy and coincidence measurements of atoms and molecules are relatively wellunderstood techniques @1‐3#. Coupled with the high bright