Discrete–variational Xα calculations of graphite and alkali–metal graphite intercalation compounds

Abstract

First-principles molecular orbital calculations using discrete–variational (DV)- Xα method are carried out on the model clusters of graphite and alkali–metal graphite intercalation compounds MC x (M=Li, Na, K, Rb, and Cs). Results of the calculations are used so as to simulate the experimentally observed near-edge X-ray-absorption fine-structures (XANES) and ultraviolet photoelectron spectra. For the clusters of graphite and KC x , the calculated partial electronic densities of states (PDOSs) are in good agreement with the experimental C K-edge and K K-edge XANES spectra, respectively. Furthermore, the accordance between the calculated DOSs and the observed UPS spectra of graphite and RbC x is also satisfactory. It is shown that the Fermi level is pushed up into the conduction band of graphite by doping alkali metals.