Coherent X-Ray Raman Spectroscopy: A Nonlinear Local Probe for Electronic Excitations

Nonlinear x-ray four-wave mixing experiments are becoming feasible due to rapid advances in high harmonic generation and synchrotron radiation coherent x-ray sources. By tuning the difference of two x-ray frequencies across the valence excitations, it is possible to probe the entire manifold of molecular electronic excitations. We show that the wave vector and frequency profiles of this x-ray analogue of coherent Raman spectroscopy provide an excellent real-space probe that carries most valuable structural and dynamical information, not available from spontaneous Raman techniques.