First observation of vibrations in core-level photoelectron spectra of free neutral molecular clusters

Core-level photoelectron spectra of free neutral methane clusters have been recorded. These spectra exhibit well-resolved surface and bulk features as well as vibrational fine structure. The vibrational structure in the cluster signal is well reproduced by a theoretical model that assumes independent contributions from inter- and intramolecular modes. The intramolecular contribution to the vibrational lineshape is taken to be equal to that of the monomer in the gas phase, while the intermolecular part is simplified to line broadening. An estimate of the cluster size has been made on the basis of the observed surface-to-bulk intensity ratio.