Adsorption of benzene on the Si(100) surface is studied from first principl
es. We find that the most stable configuration is a tetra-sigma-bonded stru
cture characterized by one C-C double bond and four C-Si bonds. A similar s
tructure: obtained by rotating the benzene molecule by 90 degrees, lies sli
ghtly higher in energy. However, rather narrow wells on the potential-energ
y surface characterize these adsorption configurations. A benzene molecule
impinging on the Si surface is most likely to be adsorbed in one of three d
ifferent di-sigma-bonded, metastable structures, characterized by two C-Si
bonds, and eventually converts into the lowest-energy configurations. These
results are consistent with recent experiments.