Theory for the nonlinear optical response of transition metals: Polarization dependence as a fingerprint of the electronic structure at surfaces and interfaces

We show that the nonlinear optical response reflects sensitively the electronic structure of transition-metal surfaces and interfaces. d and s electrons may contribute rather differently to the second-harmonic-generation (SHG) signal. This results from the different sensitivity of d and s electrons to surface and symmetry changes. Consequently, SHG for noble metals shows a by far larger dependence on the polarization of the incoming light than for transition metals like Fe, Co, Ni, in particular at lower frequencies. The theroetical results are compared with recent measurements. We conclude that the SHG yield is, in addition to the nonlinear magneto-optical Kerr effect, a sensitive fingerprint of the electronic structure at surfaces and interfaces.