A Kohn-Sham approach is presented for analyzing the many-body properti
es of LCAO Hamiltonians. The total electronic energy of the system is
shown to be a function of the different orbit al occupancies. Then an
exchange-correlation potential is introduced for each orbital, taking
into account extra-atomic and intra-atomic many-body effects. Using th
is potential, the total energy can be obtained by calculating self-con
sistently the orbital occupancies, avoiding the use of a local represe
ntation as is done in the conventional LDA calculations. The method is
applied to the calculation of the chemisorption energy and the charge
transfer for the deposition of Na on Al(100), and the interaction of
H with the GaAs(110) surface. Hydrogen is shown to passivate GaAs(110)
surfaces for a monolayer deposition.