Resonant Circular Dichroism of Chiral Metal-Organic Complex

A sizable enhancement of the circular dichroism in photoelectron spectroscopy has been measured and computed for the metal complex ?-cobalt(III) tris-acetylacetonate highest occupied molecular orbital state in the region of the Co 3p->3d Fano resonance. In the resonance the dichroism reaches the maximum value of 5% and even changes its sign as compared to the direct photoionization channel. We ascribe this enhancement to electron correlation processes, namely, with the coupling between discrete excitations and the continuum, which is correctly described in the time dependent density functional theory (TDDFT) framework. These findings open new physical aspects of photoelectron circular dichroism that now can be interpreted not only via the simple direct ionization, but also through more complex electron correlation processes.