Gas-to-solid shift of C 1s-excited benzene

Abstract

The gas-to-solid shift of benzene is reported in the C 1s-core level regime, where the C 1s → π*-transition is investigated between 284.0 eV and 286.5 eV. Simultaneous experiments on the gas phase and condensed species are used to determine the gas-to-solid shift within an accuracy of ±5 meV. Specifically, it is observed that the vibrationally resolved C 1s → π*-transition in solid benzene is red-shifted by 55 ± 5 meV relative to the transition of the isolated molecule. Contrary to previously reported experimental data and estimates this gas-to-solid shift is somewhat smaller than the gas-to-cluster shift. It is significantly smaller than that determined in previous work on gaseous and condensed benzene. These results are discussed in terms of structural properties of molecular clusters and solid benzene by involving ab initio calculations as well as processes leading to spectral shifts of core-excited variable size matter. Finally, changes in the shape of the C 1s → π*-band upon the formation of solid benzene and benzene clusters are discussed.