Linear Dichroism in Resonant Inelastic X-Ray Scattering to Molecular Spin-Orbit States
R. Guillemin1,2, S. Carniato1,2, W. C. Stolte3,4, L. Journel1,2, R. Taïeb1,2, D.W. Lindle3, and M. Simon1,2
 Schematic representation of linear dichroism observed in KL x-ray emission. Coupling between the spin-orbit interaction and the molecular field, oriented along the chemical bond, leads to different spin-orbit ratios as a function of the angle between the incoming and outgoing photons polarization. |
Using the polarimeter capabilities of our x-ray spectrometer, we have recently measured the polarization of x-ray photons emitted in a molecular core-to-core transition accompanying resonant inelastic x-ray scattering (RIXS). In this study, we have measured KL emission spectra corresponding to the filling of a 1s core hole by a 2p core electron following core-hole excitation Cl(1s)-1→(11a1)1 in CF3Cl, and Cl(1s)-1→(6σ)1 in HCl (hν=2823,5 eV in both cases). We have observed a linear dichroism in polarized x-ray-emission spectra. In a combined experimental and theoretical effort, we showed this effect is sensitive to coupling between the molecular field (MF) and spin-orbit interactions and interpreted the observed dichroism in terms of population differences in the 2px;y;z inner-shell orbitals. Polarized RIXS offers a unique opportunity to determine spin-orbit-component populations, providing a new probe of MF effects on electronic structure.
1UPMC Univ Paris 06, UMR 7614, Laboratoire de Chimie
Physique Matière et Rayonnement, F-75005 Paris, France
2CNRS, UMR 7614, Laboratoire de Chimie Physique Matière
et Rayonnement, F-75005 Paris, France
3Department of Chemistry, University of Nevada, Las Vegas,
Nevada 89154-4003, USA
4Advanced Light Source, Lawrence Berkeley National Laboratory,
Berkeley, California 94720, USA
Work performed on ALS Beamline 9.3.1
Citation: R. Guillemin, S. Carniato, W.C. Stolte, L. Journel, R. Taïeb, D.W. Lindle, and M. Simon, Phys. Rev. Lett. 101, 133003 (2008)