Journal of Physical Chemistry A, Vol.109, No.48, 10886-10896, 2005
Inner shell excitation spectroscopy of biphenyl and substituted biphenyls: Probing ring-ring delocalization
Quantitative optical oscillator strength spectra for C is excitation and ionization of gas-phase biphenyl, decafluorobiphenyl, and 2,2'-bis(bromomethyl)-1,1'-biphenyl have been derived from electron energy loss spectroscopy recorded under electric dipole dominated conditions. The C Is X-ray absorption spectrum of hexaphenylbenzene has been recorded in the solid state. The C Is spectral features are interpreted with the aid of ab initio calculations for core excitation of benzene, biphenyl, hexafluorobenzene, and decafluorobiphenyl. A weak feature at 287.7 eV in biphenyl is identified as a C 1s -> pi*(deloc) transition, characteristic of ring-ring delocalization. Its intensity and position are shown to be related to the average torsion angle and thus the extent of pi-pi-interaction between adjacent aromatic rings. The effects of perfluoro substitution on core excitation spectra are also characterized and discussed.