Effect of Spin Polarization for Hydrogen Adsorbed on Si(111)(1× 1) Surface: First-Principles Calculations

The role of spin polarization on adsorption of atomic and molecular hydrogen on Si(111)(1× 1) surface is examined by comparing the results of the local spin density approximation (LSD) and those of the local density approximation (LDA). A large improvement of the adsorption energies (around 0.8 eV/H) was found for the H atom adsorbed on Si(111)(1× 1) surface. The inclusion of spin polarization reduces the overbinding between the H atom and the silicon surface and its effect is much more pronounced when the H atom is far away from the surface. Despite of the large changes in the adsorption energies, the main character of the potential energy surface of the H atom on Si(111)(1× 1) surface is retained. An opposite effect is found in the charge-density-transfer map of LSD results as compared to LDA results for the H atom approaching the surface through the H3 path, in which the H atom loses electrons rather than gains electrons from the surface. The fact that the H atom tends to lose electrons in the silicon bulk has already been reported by the experimental studies for the behavior of the H atom in the p-type silicon. For the molecular hydrogen on Si(111)(1 × 1) surface, the effect of the spin polarization is so small that it can be neglected. c © 2000 John Wiley & Sons, Inc. Int J Quantum Chem 79: 47–55, 2000