Specific chemical bond relaxation unraveled by analysis of shake-up satellites in the oxygen single site double core hole spectrum of CO2

Abstract

We recently developed [A. Ferté, et al., J. Phys. Chem. Lett., 2020, 11, 4359] a method to compute single site double core hole (ssDCH or K⁻²) spectra. We refer to that method as NOTA+CIPSI. In the present paper this method is applied to the O K⁻² spectrum of the CO₂ molecule, and we use this as an example to discuss in detail its convergence properties. Using this approach, theoretical spectra in excellent agreement with the experimental one are obtained. Thanks to a thorough interpretation of the shake-up states responsible for the main satellite peaks and through comparison with the O K⁻² spectrum of CO, we can highlight the clear signature of the two non-equivalent carbon oxygen bonds in the oxygen ssDCH CO₂ dication.