MP2-Based Composite Extrapolation Schemes Can Predict Core-Ionization Energies for First-Row Elements with Coupled-Cluster Level Accuracy

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-08, Vol.128 (33), p.6989-6998
• Main Authors: Morgunov, Anton, Tran, Henry K., Meitei, Oinam Romesh, Chien, Yu-Che, Van Voorhis, Troy
• Format: Article
• Language: English
• Subjects: A: New Tools and Methods in Experiment and Theory
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c01606

X-ray photoelectron spectroscopy (XPS) measures core–electron binding energies (CEBEs) to reveal element-specific insights into the 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 limit of CEBEs from ΔMP2 and ΔCC energies across 94 K-edges in diverse organic molecules. We demonstrate that an alternative composite scheme using ΔMP2 in a large basis corrected by ΔCC-ΔMP2 difference in a small basis can quantitatively recover optimally extrapolated ΔCC CEBEs within 0.02 eV. Unlike ΔCC, MP2 calculations do not suffer from convergence issues and are computationally cheaper, and thus, the composite ΔMP2/ΔCC 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 data.