A comprehensive photoabsorption, photoionization, and shake-up excitation study of the C 1s cross section of benzene

• Published in: The Journal of chemical physics 2000-11, Vol.113 (17), p.7362-7375
• Main Authors: Rennie, E. E., Kempgens, B., Köppe, H. M., Hergenhahn, U., Feldhaus, J., Itchkawitz, B. S., Kilcoyne, A. L. D., Kivimäki, A., Maier, K., Piancastelli, M. N., Polcik, M., Rüdel, A., Bradshaw, A. M.
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.1290029

The absolute photoabsorption cross section of benzene (C6H6), encompassing the C 1s−1 π*e2u resonance, the C 1s threshold, the satellite thresholds, and extending up to 800 eV, has been measured using synchrotron radiation. Measurements of the discrete absorption structure from below the C 1s ionization threshold have been performed at high resolution. In order to unambiguously assign all structure present in the photoabsorption cross section, C 1s photoelectron spectra were measured from the C 1s threshold region up to 350 eV along with satellite spectra. The C 1s−1 single-hole and the satellite cross sections have been derived in absolute units, and their angular distributions have been determined. Resonant and normal Auger spectra were taken on the main features of the photoabsorption and single-hole cross sections. From the best resolved photoelectron spectra the underlying structure in the asymmetric benzene photoelectron peak can be partly disentangled. The experimental data show that at least two vibrational modes play a role in the C 1s photoelectron spectrum. The behavior of the investigated shake-up structure closely resembles that of ethene and ethyne, where the satellite bands due to π→π* excitations gain intensity towards threshold, an observation which may be attributed to conjugate shake-up processes. These processes lead to a significant contribution of the satellite intensity to the production of the absorption features traditionally assigned to the carbon shape resonances in benzene. An EXAFS analysis of the wide range oscillations present on the photoabsorption cross section has been performed, and reveals the C–C nearest-neighbor distance.