title: Multidimensional x-ray spectroscopy of valence and core excitations in cysteine.
abstract: 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 [Formula: see text] and [Formula: see text] 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.
authors: Department of Chemistry, University of California, 450 Rowland Hall, Irvine, California 92697, USA.
authors: Jason D
authors: JD
authors: Biggs
authors: Department of Chemistry, University of California, 450 Rowland Hall, Irvine, California 92697, USA.
authors: Yu
authors: Y
authors: Zhang
authors: Department of Chemistry, University of California, 450 Rowland Hall, Irvine, California 92697, USA.
authors: Daniel
authors: D
authors: Healion
authors: Department of Chemistry, University of California, 450 Rowland Hall, Irvine, California 92697, USA.
authors: Shaul
authors: S
authors: Mukamel
mesh_terms: D003545:Cysteine / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D056928:X-Ray Absorption Spectroscopy
chemical_list: D003545:Cysteine; D009584:Nitrogen; D010100:Oxygen