School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.
J Chem Theory Comput. 2021 Jun 8;17(6):3644-3651. doi: 10.1021/acs.jctc.1c00171. Epub 2021 May 27.
The capability to determine core-electron binding energies (CEBEs) is vital in the analysis of X-ray photoelectron spectroscopy, and the continued development of light sources has made inner shell spectroscopy of heavier elements increasingly accessible. Density functional theory is widely used to determine CEBEs of lighter elements (boron-fluorine). It is shown that good performance of exchange-correlation functionals for these elements does not necessarily translate to the calculation of CEBEs for the heavier elements from the next row of the periodic table, and in general, larger errors are observed. Two strategies are explored that improve the accuracy of the calculated CEBEs. The first is to apply element and functional dependent energy corrections, and the second is a reparametrization of a short-range corrected functional. This functional is able to reproduce experimental phosphorus and sulfur K-edge CEBEs with an average error of 0.15 eV demonstrating the importance of reducing the self-interaction error associated with the core electrons and represents progress toward a density functional theory calculation that performs equally well for ionization at the K-edge of all elements.
确定芯电子结合能 (CEBE) 的能力对于 X 射线光电子能谱分析至关重要，而光源的不断发展使得更重元素的内壳光谱变得越来越容易获得。密度泛函理论被广泛用于确定较轻元素（硼-氟）的 CEBE。研究表明，对于这些元素的交换相关泛函的良好性能不一定转化为计算周期表下一周期较重元素的 CEBE，并且通常会观察到更大的误差。探索了两种提高计算 CEBE 准确性的策略。第一种是应用元素和函数相关的能量校正，第二种是对短程校正函数进行重新参数化。该函数能够以平均误差 0.15eV 重现实验磷和硫 K 边 CEBE，表明减少与芯电子相关的自相互作用误差的重要性，并代表朝着为所有元素 K 边的电离都能同样良好地执行的密度泛函理论计算取得进展。
