Partial Ion Yield Sspectroscopy around the Cl 2p and C 1s Ionization Thresholds in CF3Cl

We present a partial ion yield experiment on freon 13, CF3Cl, excited in the vicinity of the C 1s and Cl 2p ionization thresholds. We have collected a large amount of cationic fragments and a few anionic fragments at both edges. We have observed a strong intensity dependence of Rydberg transitions with ion fragment size for the CFnCl+ and CFn+/F+ (n=0–3) series at both the Cl 2p and C 1s ionization edges. Selectivity in the fragmentation processes involving the C–Cl and C–F bonds are highlighted by the intensities of the C 1s to lowest unoccupied molecular orbital (LUMO) and LUMO+1 transitions measured on the CFnCl+ and CFn+ yields. Equally, by comparison with their cation counterpart, we discuss possible bond-length dependence for the anion formation at the carbon 1s edge

K-shell x-ray spectroscopy of atomic nitrogen

Absolute {\it K}-shell photoionization cross sections for atomic nitrogen have been obtained from both experiment and state-of-the-art theoretical techniques. Due to the difficulty of creating a target of neutral atomic nitrogen, no high-resolution {\it K}-edge spectroscopy measurements have been reported for this important atom. Interplay between theory and experiment enabled identification and characterization of the strong $1s$ $\rightarrow$ $np$ resonance features throughout the threshold region. An experimental value of 409.64 $\pm$ 0.02 eV was determined for the {\it K}-shell binding energy.Comment: 4 pages, 2 graphs, 1 tabl

Low-Energy Nondipole Effects in Molecular Nitrogen Valence-Shell Photoionization

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 3sigmag, 1piu, and 2sigmau shells of N2 exhibit spectral variations with incident photon energies from thresholds to ~200 eV which are attributed via concomitant calculations to particular final-state symmetry waves arising from (E1)[direct-product](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

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 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.Comment: 4 pages, 3 figure

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

Molecular-orbital Studies Via Satellite-free X-ray Fluorescence: Cl-K Absorption and K–Valence-level Emission Spectra of Chlorofluoromethanes

X-ray absorption and emission measurements in the vicinity of the chlorine K edge of the three chlorofluoromethanes have been made using monochromatic synchrotron radiation as the source of excitation. By selectively tuning the incident radiation to just above the Cl 1s single-electron ionization threshold for each molecule, less complex x-ray-emission spectra are obtained. This reduction in complexity is attributed to the elimination of multielectron transitions in the Cl K shell, which commonly produce satellite features in x-ray emission. The resulting satellite-free x-ray-emission spectra exhibit peaks due only to electrons in valence molecular orbitals filling a single Cl 1s vacancy. These simplified emission spectra and the associated x-ray absorption spectra are modeled using straightforward procedures and compared with semiempirical ground-state molecular-orbital calculations. Good agreement is observed between the present experimental and theoretical results for valence-orbital energies and those obtained from ultraviolet photoemission, and between relative radiative yields determined both experimentally and theoretically in this work

Nondipole Resonant X-ray-Raman Spectroscopy: Polarized Inelastic Scattering at the K Edge of Cl2

Experimental and theoretical studies are reported on the inelastic (Raman) scattering of wavelength-selected polarized x rays from the K edge of gas-phase chlorine molecules. The polarized emission spectra exhibit prominent nondipole features consequent of phase variations of the incident and emitted radiation over molecular dimensions, as predicted by the Kramers-Heisenberg scattering formalism. Issues pursuant to the detection of core-hole localization by resonant Raman scattering from homonuclear diatomic molecules are critically examined. [S0031-9007(97)03486-8

Reply to Comment on ‘Nondipole Resonant X-ray-Raman Spectroscopy: Polarized Inelastic Scattering at the K Edge of Cl2,’

Mills et al. Reply: In their Comment on our Letter [1], Gel’mukhanov and Ågren [2] reiterate recent assertions [3] based on their earlier theoretical studies [4]. The primary purpose of their Comment is apparently to refute our stated conclusion that core-excited-state localization/ delocalization mechanisms are irrelevant to interpretations of reported Raman scattering experiments on homonuclear diatomic molecules