交换能在强极性键的芯电子结合能建模中的作用。
The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds.
作者信息
Wang Feng, Chong Delano P
机构信息
School of Science, Computing and Emerging Technologies, Swinburne University of Technology, Melbourne, VIC 3122, Australia.
Department of Chemistry, University of British Columbia, 2016 Main Mall, Vancouver, BC V6T 1Z1, Canada.
出版信息
Molecules. 2025 Jul 7;30(13):2887. doi: 10.3390/molecules30132887.
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.
准确测定碳芯电子结合能（C1s CEBEs）对于X射线光电子能谱（XPS）分析和预测性计算建模至关重要。本研究评估了基于密度泛函理论（DFT）的计算C1s芯电子结合能（CEBEs）的方法，使用作者之一在过去十年中开发的δ自洽场ΔSCF（或ΔDFT）方法，比较了三种泛函——PW86x - PW91c（DFTpw）、mPW1PW和PBE50——在小分子烃和卤代分子（卤代烷）中的68个C1s案例。PW86x - PW91c泛函实现了0.1735 eV的均方根偏差（RMSD），使用mPW1PW和PBE50对极性C - X键（X = O、F）的准确性有所提高，将平均绝对偏差（AAD）降低至约0.132 eV。该研究强调了哈特里 - 福克（HF）交换在改进CEBE预测中的作用，并突出了理论和实验方法之间的协同作用。这些见解为机器学习（ML）驱动的光谱分析奠定了基础，通过更可靠的自动XPS分析推进材料表征和催化研究。
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