We report a spin-unrestricted density functional theory (DFT) solution at the symmetric dimer structure for cluster models of Si(100). With this solution, it is shown that the symmetric structure is a minimum on the DFT potential energy surface, although higher in energy than the buckled structure. In restricted DFT calculations the symmetric structure is a saddle point connecting the two buckled minima. To further assess the effects of electron correlation on the relative enerfies of symmetric versus buckled dimers on Si(100), multireference second order perturbation theory (MRMP2) calculations are performed on these DFT optimized minima. The symmetric structure is predicted to be lower in energy than the buckled structure via MRMP2, while the reverse order is found by DFT. The implications for recent experimental interpretations are discussed.

A simplified approach to treating the electron correlation energy is suggested in which only the alpha-beta component of the second order Moller-Plesset energy is evaluated, and then scaled by an empirical factor which is suggested to be 1.3. This scaled opposite spin second order energy (SOS-MP@) yields results for relative energies and derivative properties that are statistically improved over the conventional MP2 method. Furthermore, the SOS-MP2 energy can be evaluated without the 5th order computational steps associated with MP2 theory, even without exploiting any spatial locality. A 4th order algorithm is given for evaluating the opposite spin MP2 energy using auxiliary basis expansions, and a Laplace aproach, and timing comparisons are given.