Theoretical cluster calculations for the Si(100) surface show that the use of doubly occupied orbital wavefunctions, such as the closed‐shell Hartree–Fock (HF), lead to an asymmetric dimer description of the surface. The inclusion of electron correlation produces a symmetric dimer description with a ground state ∠1.0 eV below the minimum of the HF buckled dimer. There are two low‐lying states of the symmetric dimer (a singlet and a triplet) with very different geometries. Energy minimization calculations indicate that a (2×1) structure is favored over a c(2×2) structure. We also report ionization potentials for surface and Si(2p) core electrons that are consistent with current experimental data.