科勒 - 萨尔韦蒂公式的重新参数化 - Suppr

Baskerville Adam L, Targema Msugh, Cox Hazel

Department of Chemistry, School of Life Sciences, University of Sussex, Falmer, Brighton BN1 9QJ, UK.

R Soc Open Sci. 2022 Jan 5;9(1):211333. doi: 10.1098/rsos.211333. eCollection 2022 Jan.

We investigate the Colle-Salvetti (CS) formula, the basis of the Lee, Yang and Parr (LYP) correlation functional used in approximate density functional theory. The CS formula is reparametrized using high-accuracy Hartree-Fock (HF) wavefunctions to determine the accuracy of the formula to calculate anions. Fitting to the hydride ion or the two-electron system just prior to electron detachment at the HF level of theory does not, in general, improve the calculated correlation energies using the parameters derived from the CS/LYP method. An analysis of the CS parameters used in the popular LYP functional demonstrates the ingenuity and perhaps fortuitousness of the original formulation by CS.

我们研究了Colle-Salvetti（CS）公式，它是近似密度泛函理论中使用的Lee、Yang和Parr（LYP）相关泛函的基础。使用高精度Hartree-Fock（HF）波函数对CS公式进行重新参数化，以确定该公式计算阴离子的准确性。一般来说，在HF理论水平下，拟合氢负离子或电子脱离前的双电子体系，并不会使用从CS/LYP方法导出的参数来提高计算得到的相关能。对流行的LYP泛函中使用的CS参数进行分析，证明了CS原始公式的独创性，或许还有些偶然因素。