Several nonlinear spectroscopy experiments which employ broadband x-ray pulses to probe the coupling between localized core and delocalized valence excitation are simulated for the amino acid cysteine at the K-edges of oxygen and nitrogen and the K and L-edges of sulfur. We focus on two dimensional (2D) and 3D signals generated by two- and three-pulse stimulated x-ray Raman spectroscopy (SXRS) with frequency-dispersed probe. We show how the four-pulse x-ray signals kI=−k1+k2+k3 and kII=k1−k2+k3 can give new 3D insight into the SXRS signals. The coupling between valence- and core-excited states can be visualized in three dimensional plots, revealing the origin of the polarizability that controls the simpler pump-probe SXRS signals.
@article{arxiv.1303.4706,
title = {Multidimensional X-Ray Spectroscopy of Valence and Core Excitations in Cysteine},
author = {Jason D. Biggs and Yu Zhang and Daniel Healion and Shaul Mukamel},
journal= {arXiv preprint arXiv:1303.4706},
year = {2015}
}