Specific chemical bond relaxation unravelled by analysis of shake-up satellites in the oxygen single site double core hole spectrum of CO${}_2$

Abstract

We developed recently [A. Ferté, et al., J. Phys. Chem. Lett. 11, 4359 (2020)] 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 CO${}_2$ molecule, and we use this as an example to discuss in detail its convergence properties. Using this approach, a theoretical spectra in excellent agreement with the experimental one is obtained. Thanks to a thorough interpretation of the shake-up states responsible for the main satellite peaks and with the help of a 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 CO${}_2$ dication.

16 pages, 7 figures, 7 tables

References in corpus (2)

• Highly Accurate Prediction of Core Spectra of Molecules at Density Functional Theory Cost: Attaining sub eV Error from a Restricted Open-Shell Kohn-Sham Approach
• Molecular double core-hole electron spectroscopy for chemical analysis

Cited by in corpus (3)

• Reference Energies for Valence Ionizations and Satellite Transitions
• Anomalous propagators and the particle-particle channel: Bethe-Salpeter equation
• Radiationless decay spectrum of O 1s double core holes in liquid water