Multidimensional x-ray spectroscopy of valence and core excitations in cysteine

J Chem Phys. 2013 Apr 14;138(14):144303. doi: 10.1063/1.4799266.

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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Cysteine / chemistry*
  • Nitrogen / chemistry
  • Oxygen / chemistry
  • Spectrum Analysis, Raman*
  • X-Ray Absorption Spectroscopy

Substances

  • Cysteine
  • Nitrogen
  • Oxygen