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

First-principles molecular orbital calculations using discrete-variational (DV)-X alpha method are carried out on the model clusters of graphite and alkali-metal graphite intercalation compounds MCx(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 KCx, 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 RbCx is also satisfactory. It is shown that the Fermi level is pushed up into the conduction band of graphite by doping alkali metals. (C) 1999 Elsevier Science S.A. All rights reserved.