The Role of Exchange Energy in Modeling Core-Electron Binding Energies of Strongly Polar Bonds.

IF 4.2 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Molecules Pub Date : 2025-07-07 DOI:10.3390/molecules30132887

Feng Wang, Delano P Chong

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引用次数: 0

Abstract

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.

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交换能在模拟强极性键的核电子结合能中的作用。

碳核电子结合能（C1s - CEBEs）的准确测定对于x射线光电子能谱（XPS）的赋值和预测计算建模至关重要。本研究评估了基于密度泛函理论（DFT）计算C1s核心电子结合能（CEBEs）的方法，比较了三种功能- pw86x - pw91c (DFTpw)， mPW1PW和pbe50 -在68个小碳氢化合物和卤化分子（烷基卤化物）中的C1s案例，使用了delta自一致场ΔSCF（或ΔDFT）方法，该方法是由一位作者在过去十年中开发的。PW86x-PW91c函数实现了0.1735 eV的均方根偏差（RMSD），使用mPW1PW和PBE50提高了极性C-X键（X= 0， F）的精度，将平均绝对偏差（AAD）降低到~0.132 eV。该研究强调了Hartree-Fock （HF）交换在改进CEBE预测中的作用，并强调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、推进材料表征以及通过更可靠的自动化XPS作业进行催化奠定了基础。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Molecules 化学-有机化学

CiteScore

7.40

自引率

8.70%

发文量

7524

审稿时长

1.4 months

期刊介绍： Molecules (ISSN 1420-3049, CODEN: MOLEFW) is an open access journal of synthetic organic chemistry and natural product chemistry. All articles are peer-reviewed and published continously upon acceptance. Molecules is published by MDPI, Basel, Switzerland. Our aim is to encourage chemists to publish as much as possible their experimental detail, particularly synthetic procedures and characterization information. There is no restriction on the length of the experimental section. In addition, availability of compound samples is published and considered as important information. Authors are encouraged to register or deposit their chemical samples through the non-profit international organization Molecular Diversity Preservation International (MDPI). Molecules has been launched in 1996 to preserve and exploit molecular diversity of both, chemical information and chemical substances.