X-ray natural circular dichroism in a uniaxial gyrotropic single crystal of LiIO3

We produce the first experimental evidence of x-ray natural circular dichroism (XNCD) in a uniaxial gyrotropic crystal of α-LiIO3 that is known to crystallize with space group P63 and to exhibit a very strong nonlinear susceptibility. For the sake of simplicity, the optical axis was set colinear to the direction of the exciting x-ray beam in order to get rid of undesirable birefringence and linear dichroism effects. The nicely structured XNCD spectra recorded at the LI, LII, and LIII edges of iodine are assigned to the electric dipole–electric quadrupole (E1.E2) interference terms which do not vanish in gyrotropic crystals but contribute to a second order polarizability. Our interpretation is consistent with a band structure calculation and is fully supported by ab initio multiple scattering simulations. The signatures recorded at the LII and LIII edges are similar and have the same sign. This is in contrast to x-ray magnetic circular dichroism (XMCD) spectra which usually exhibit opposite signs at the LII and LIII edges: while the exchange and spin-orbit interactions are the driving terms in XMCD, this is not the case in XNCD. The XNCD signal detected at the LI edge is found to be relatively more intense and has the opposite sign. These results leave very little space for a contribution of the electric dipole–magnetic dipole (E1.M1) interference terms which are usually dominant at optical wavelengths but should be barely detectable in the x-ray range.