Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 24, Issue 8, Pages 4769-4784Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cp05476g
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Funding
- National Science Foundation [CHE-2044648, PAS1583, PAS1963.175]
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We present a new theoretical approach for simulating X-ray photoelectron spectra of strongly correlated molecular systems, which combines multireference algebraic diagrammatic construction theory with a core-valence separation technique. The results demonstrate that this approach is more accurate and reliable for systems with a multireference character and has a low computational cost.
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.
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