Localized excitons and breaking of chemical bonds at III-V (110) surfaces.

Electron-hole excitations in the surface bands of GaAs (110) are analyzed using constrained density-functional theory calculations. The results show that Frenkel-type autolocalized excitons are formed. The excitons induce a local surface unrelaxation which results in a strong exciton-exciton attraction and makes complexes of two or three electron-hole pairs more favorable than separate excitons. In such microscopic exciton “droplets” the electron density is mainly concentrated in the dangling orbital of a surface Ga atom whereas the holes are distributed over the bonds of this atom to its As neighbors thus weakening the bonding to the substrate. This finding suggests the microscopic mechanism of a laser-induced emission of neutral Ga atoms from GaAs and GaP (110) surfaces. 73.20.At, 71.35.+z, 71.38.+i, 79.20.Ds Typeset using REVTEX