MP2-based composite extrapolation schemes can predict core-ionization energies for first-row elements with coupled-cluster level accuracy

• URL: http://arxiv.org/abs/2403.06364v1
• Date: Mon, 11 Mar 2024 01:27:57 GMT
• Title: MP2-based composite extrapolation schemes can predict core-ionization energies for first-row elements with coupled-cluster level accuracy
• Authors: Anton Morgunov, Henry K. Tran, Oinam Romesh Meitei, Yu-Che Chien, Troy Van Voorhis
• Abstract summary: X-ray photoelectron spectroscopy (XPS) measures core-electron binding energies (CEBEs) to reveal element-specific insights into chemical environment and bonding. This work systematically investigates basis set selection for extrapolation to the complete basis set (CBS) limit of CEBEs. An alternative composite scheme using $Delta$MP2 in a large basis corrected by $Delta$CC-$Delta$MP2 difference in a small basis can quantitatively recover optimally extrapolated $Delta$CC CEBEs within 0.02 eV.
• Score: 0.0
• License: http://creativecommons.org/licenses/by/4.0/
• Abstract: X-ray photoelectron spectroscopy (XPS) measures core-electron binding energies (CEBEs) to reveal element-specific insights into chemical environment and bonding. Accurate theoretical CEBE prediction aids XPS interpretation but requires proper modeling of orbital relaxation and electron correlation upon core-ionization. This work systematically investigates basis set selection for extrapolation to the complete basis set (CBS) limit of CEBEs from $\Delta$MP2 and $\Delta$CC energies across 94 K-edges in diverse organic molecules. We demonstrate that an alternative composite scheme using $\Delta$MP2 in a large basis corrected by $\Delta$CC-$\Delta$MP2 difference in a small basis can quantitatively recover optimally extrapolated $\Delta$CC CEBEs within 0.02 eV. Unlike $\Delta$CC, MP2 calculations do not suffer from convergence issues and are computationally cheaper, and, thus, the composite $\Delta$MP2/$\Delta$CC scheme balances accuracy and cost, overcoming limitations of solely using either method. We conclude by providing a comprehensive analysis of the choice of small and large basis sets for the composite schemes and provide practical recommendations for highly accurate (within 0.10-0.15 eV MAE) ab initio prediction of XPS spectra.

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