The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds
Accurate determination of carbon core-electron binding energies (C1s CEBEs) is crucial for X-ray photoelectron spectroscopy (XPS) assignments and predictive computational modeling. This study evaluates density functional theory (DFT)-based methods for calculating C1s core-electron binding energies (...
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2025-07-01
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| author | Feng Wang Delano P. Chong |
| author_facet | Feng Wang Delano P. Chong |
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| description | Accurate determination of carbon core-electron binding energies (C1s CEBEs) is crucial for X-ray photoelectron spectroscopy (XPS) assignments and predictive computational modeling. This study evaluates density functional theory (DFT)-based methods for calculating C1s core-electron binding energies (CEBEs), comparing three functionals—PW86x-PW91c (DFTpw), mPW1PW, and PBE50—across 68 C1s cases in small hydrocarbons and halogenated molecules (alkyl halides), using the delta self-consistent field ΔSCF (or ΔDFT) method developed by one of the authors over the past decade. The PW86x-PW91c functional achieves a root mean square deviation (RMSD) of 0.1735 eV, with improved accuracy for polar C-X bonds (X=O, F) using mPW1PW and PBE50, reducing the average absolute deviation (AAD) to ~0.132 eV. The study emphasizes the role of Hartree–Fock (HF) exchange in refining CEBE predictions and highlights the synergy between theoretical and experimental approaches. These insights lay the groundwork for machine learning (ML)-driven spectral analysis, advancing materials characterization, and catalysis through more reliable automated XPS assignments. |
| format | Article |
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| institution | Kabale University |
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| publishDate | 2025-07-01 |
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| spelling | doaj-art-f7f888ad1d4249b18e1e657dd4e4ddda2025-08-20T03:28:32ZengMDPI AGMolecules1420-30492025-07-013013288710.3390/molecules30132887The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar BondsFeng Wang0Delano P. Chong1School of Science, Computing and Emerging Technologies, Swinburne University of Technology, Melbourne, VIC 3122, AustraliaDepartment of Chemistry, University of British Columbia, 2016 Main Mall, Vancouver, BC V6T 1Z1, CanadaAccurate determination of carbon core-electron binding energies (C1s CEBEs) is crucial for X-ray photoelectron spectroscopy (XPS) assignments and predictive computational modeling. This study evaluates density functional theory (DFT)-based methods for calculating C1s core-electron binding energies (CEBEs), comparing three functionals—PW86x-PW91c (DFTpw), mPW1PW, and PBE50—across 68 C1s cases in small hydrocarbons and halogenated molecules (alkyl halides), using the delta self-consistent field ΔSCF (or ΔDFT) method developed by one of the authors over the past decade. The PW86x-PW91c functional achieves a root mean square deviation (RMSD) of 0.1735 eV, with improved accuracy for polar C-X bonds (X=O, F) using mPW1PW and PBE50, reducing the average absolute deviation (AAD) to ~0.132 eV. The study emphasizes the role of Hartree–Fock (HF) exchange in refining CEBE predictions and highlights the synergy between theoretical and experimental approaches. These insights lay the groundwork for machine learning (ML)-driven spectral analysis, advancing materials characterization, and catalysis through more reliable automated XPS assignments.https://www.mdpi.com/1420-3049/30/13/2887C1s core-electron binding energy (CEBE)density functional theory (DFT) computationsPW86x-PW91cmPW1PW and PBE50 functionalsexchange energyX-ray photoelectron spectra (XPS) |
| spellingShingle | Feng Wang Delano P. Chong The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds Molecules C1s core-electron binding energy (CEBE) density functional theory (DFT) computations PW86x-PW91c mPW1PW and PBE50 functionals exchange energy X-ray photoelectron spectra (XPS) |
| title | The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds |
| title_full | The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds |
| title_fullStr | The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds |
| title_full_unstemmed | The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds |
| title_short | The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds |
| title_sort | role of exchange energy in modeling core electron binding energies of strongly polar bonds |
| topic | C1s core-electron binding energy (CEBE) density functional theory (DFT) computations PW86x-PW91c mPW1PW and PBE50 functionals exchange energy X-ray photoelectron spectra (XPS) |
| url | https://www.mdpi.com/1420-3049/30/13/2887 |
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