T. Darrah Thomas

X‐Ray Photoelectron Spectroscopy of Alkali Halides

We have measured ionization potentials for the removal of various electrons from the alkali chlorides and the sodium and cesium halides. These binding energies are compared with the predictions of a simple point charge model with and without corrections for polarization and repulsion. The simple model predicts and the data show that the spacings of the energy levels for a given ion are independent of what crystal it is in and are the same as for the free ion. The point charge model also allows us to calculate the difference between cation and anion energy levels in the same crystal. There is, however, a disagreement between the predicted and experimental values of this difference that ranges from about 1.8 eV for LiCl to −0.2 eV for RbCl. This discrepancy is markedly reduced by inclusion of polarization effects. The point charge model with polarization and repulsion corrections predicts absolute ionization potentials for the alkali and halide ions that differ in a systematic way from those observed. For t...

Accurate core ionization potentials and photoelectron kinetic energies for light elements

Abstract By electron spectroscopy we have determined accurate values for the neon 1s ionization potential (870.312±.017 eV) and the neon Auger ( 1 D 2 ) k

Vibrational structure in the carbon 1s ionization of hydrocarbons: Calculation using electronic structure theory and the equivalent-cores approximation

A simple ab initio procedure is used to calculate the vibrational structure observed in the carbon 1s ionization of seven hydrocarbons (methane, deuteromethane, ethane, ethene, deuteroethene, ethyne, and deuteroethyne), with good agreement between experiment and theory. The method involves use of the equivalent-cores approximation, localized holes in molecules with equivalent carbons, and the harmonic oscillator approximation. The approach provides insight into the vibrational modes of the core-ionized molecules. It is potentially useful in extracting carbon 1s ionization energies from spectra from molecules having inequivalent carbons or in finding information on inner-hole lifetimes from inner-shell spectra.

Carbon 1s photoelectron spectroscopy of CF4 and CO: Search for chemical effects on the carbon 1s hole-state lifetime

Carbon 1s photoelectron spectra for CF4 and CO have been measured at several photon energies near the carbon 1s threshold. The spectra have been analyzed in terms of the vibrational structure and the natural linewidth. For CO the vibrational structure shows evidence for anharmonicity in both the energy spacing and the intensity. Analysis of the results using an anharmonic model gives an equilibrium bond length for core-ionized CO that is 4.85 pm shorter than that of neutral CO. For CF4, the vibrational structure is very weak, and the analysis shows that the change in equilibrium CF bond length upon ionization is no more than 0.54 pm. Ab initio theoretical calculations give results in accord with these bond-length changes. The unusually small bond-length contraction in CF4 can be understood in terms of nonbonded fluorine–fluorine repulsion. The natural linewidth for core-ionized CO, 95±5 meV, is essentially the same as that of CH4. This result is in contrast with expectations based on the one-center model ...

Non-dipole excitation of core holes by electron impact. Multiplet splitting in CO and N2

Abstract Low-energy electron impact leads to non-dipole excitation of core electrons to triplet states. The multiples splitting in CO is in agreement with theory and shows that the 2π orbital is localized predominantly on the carbon. The splitting affects both energy-loss and Auger spectra of CO and N 2 .

Localized states in molecular auger spectra

Abstract The influence of the degree of localization of the two final holes on the Auger spectra of a simple diatomic molecule is analysed in detail and cases where such effects may be observed experimentally are discussed. The results are compared with studies of the valence band Auger spectra of solids.

HIGH RESOLUTION PHOTOELECTRON SPECTROSCOPY OF SULFUR 2P ELECTRONS IN H2S, SO2, CS2, AND OCS

High‐resolution photoelectron spectra for the 2p electrons in H2S, SO2, CS2, and OCS show the effects of vibrational excitation in the core‐excited species as well as the splitting of the 2p3/2 hole state by the molecular field. Theoretical calculations at the Hartree–Fock level account reasonably well for the vibrational structure. The molecular‐field splitting is calculated with a configuration interaction‐based method using large basis sets. This produces values for the 2p3/2 splitting of 108, 96, 129, and 144 meV for the title molecules, to be compared with experimental values of 110, 105, 140, and 150 meV. Thus all observed features in the spectra are quantitatively accounted for by theoretical modeling.

Recoil excitation of vibrational structure in the carbon 1s photoelectron spectrum of CF4

The carbon 1s photoelectron spectrum of CF4 measured at photon energies from 330 to 1500 eV shows significant contributions from nonsymmetric vibrational modes. These increase linearly as the photon energy increases. The excitation of these modes, which is not predicted in the usual Franck-Condon point of view, arises from the recoil momentum imparted to the carbon atom in the ionization process. A theory is presented for quantitative prediction of the recoil effect; the predictions of this theory are in agreement to the measurements. The experiments also yield the vibrational frequencies of the symmetric and asymmetric stretching modes in core-ionized CF4, the change in CF bond length upon ionization, -0.61 pm, and the Lorentzian linewidth of the carbon 1s hole, 67 meV.

Equivalent-cores analysis of esca shifts of fluorine 1s electrons

Abstract The assumption of equivalent cores suggested by Jolly to relate core-electron binding-energy shifts to thermochemical quantities has appeared to be invalid for fluorine containing compounds. We show that previously neglected corrections account for the discrepancy.

Additivity of substituent effects. Core-ionization energies and substituent effects in fluoromethylbenzenes.

Carbon 1s ionization energies have been measured for all of the carbon atoms in eight fluoromethylbenzenes. Enthalpies of protonation have been calculated for protonation at all of the ring carbons in the same molecules. These data together with previously reported data on fluorobenzenes and methylbenzenes provide the basis for studying the additivity of substituent effects and the correlation between enthalpies of protonation with core-ionization energies. Although a linear additivity model accounts reasonably well for both the ionization energies and the enthalpies of protonation, a better description, especially for the enthalpies, is obtained by inclusion of nonlinear terms that account for interactions between two substituents on the same molecule. There are families of nearly parallel correlation lines between enthalpies of protonation and core-ionization energies. The existence of several families can be primarily understood in terms of the linear additivity picture and more completely understood when the nonlinear terms are taken into account. The role of the methyl group as a polarizible pi-electron donor is contrasted with the role of fluorine, which is a substituent of low polarizibility that acts to withdraw electrons from the adjacent carbon and to donate electrons through resonance to the ring. The role of the hydrogen atoms as pi-electron acceptors in the protonated species is illustrated.