Simulating X-ray photoelectron spectra with strong electron correlation using multireference algebraic diagrammatic construction theory.

We present a new theoretical approach for the simulations of X-ray photoelectron spectra of strongly correlated molecular systems that combines multireference algebraic diagrammatic construction theory (MR-ADC) [ J. Chem. Phys. , 2018, 149 , 204113] with a core-valence separation (CVS) technique. The resulting CVS-MR-ADC approach has a low computational cost while overcoming many challenges of the conventional multireference theories associated with the calculations of excitations from inner-shell and core molecular orbitals. Our results demonstrate that the CVS-MR-ADC methods are as accurate as single-reference ADC approximations for predicting core ionization energies of weakly-correlated molecules, but are more accurate and reliable for systems with a multireference character, such as a stretched nitrogen molecule, ozone, and isomers of the benzyne diradical. We also highlight the importance of multireference effects for the description of core-hole screening that determines the relative spacing and order of peaks in the XPS spectra of strongly correlated systems.