Role of electronic versus atomic relaxations in Stokes shifts at defects in solids

Redshifts of luminescence relative to optical absorption bands (Stokes shifts) of molecules and of defects in solids are universally attributed to slow atomic relaxations on the grounds that electronic transitions are fast (Franck-Condon principle). Here we report a novel phenomenon that can occur only in the solid state: Stokes shifts caused by slow electronic relaxations. We demonstrate that the phenomenon occurs in the nonbridging oxygen defect in amorphous SiO2. We predict that another defect (OH group), which can exist in either crystalline or amorphous SiO2, has a similar Stokes shift, but it arises from a mix of lattice and electronic relaxations with manifest differences in the two phases.