Photoemission from hybrid states of Cl@C60 before and after a stabilizing charge transfer

Abstract

Photoionization calculations of the endofullerene molecule Cl@C60 with an open-shell chlorine atom are performed in the linear response density functional theory based on a spherical jellium model of C60. Cross sections for atom–fullerene hybrid photoemission studied show the effects of the hybridization symmetry, the giant plasmon and the molecular cavity. Comparisons with the results of Ar@C60 provide insights into the role of a shell-closing electron and its influence on the dynamics. The results for Cl@C60 are further compared with those of a more stable configuration that results after a C60 electron transfers to Cl forming Cl−@. This comparison reveals noticeable differences in the ionization properties of the antibonding hybrid state while the bonding hybrid remains nearly unaltered showing a magnification covering the entire giant plasmon energy range. These predictions should raise interest in probing the molecular configuration using photoelectron spectroscopy.