Experimental and theoretical investigation of molecular field effects by polarization-resolved resonant inelastic x-ray scattering

Abstract

We present a combined theoretical and experimental study of molecular field effects on molecular core levels. Polarization-dependent resonant inelastic x-ray scattering is observed experimentally after resonant $K$-shell excitation of ${\text{CF}}_{3}\text{Cl}$ and HCl. We explain the linear dichroism observed in spin-orbit level intensities as due to molecular field effects, including singlet-triplet exchange, and interpret this behavior in terms of population differences in the $2{p}_{x,y,z}$ inner-shell orbitals. We investigate theoretically the different factors that can affect the electronic populations and the dynamical $R$ dependence of the spin-orbit ratio. Finally, the results obtained are used to interpret the $L$-shell absorption spectra of the two molecules.