Dataset for paper: Consequences of approximating electron correlation effects

Data for paper published in Molecular Physics Nov 2022 The zip file contains 7 subdirectories containing (i) optimised wavefunctions (ii) static Coulomb hole data (fig 3), (iii) dynamic Coulomb hole data (fig 4 &amp; 5), (iv) ‘exact’ electron correlation energy data (fig 6) (v) energy density data as a function of the intracule coordinate r (fig 7), (vi) energy density data as a function of the extracule coordinate R (fig 8), (vii) radial electron correlation energy distribution data using CS and LYP functional (fig 9). For more information about the data, please see the Data_readme_notes file in the zip folder. All data files (pd, sv, txt) are text files so can be opened in any text editor. Also included in some directories are the Latex files (.tex) used to generate the figures in the manuscript. This requires Latex software/editor. Abstract The effect of approximating electron correlation in few-electron systems is investigated using three wavefunctions: the many body wavefunction referred to as fully-correlated (FC), the Hartree Fock wavefunction (HF), and the Colle and Salvetti Jastrow-style wavefunction (CS) used in the derivation of the popular Lee, Yang and Parr (LYP) correlation functional. The electron correlation energy, static and dynamic Coulomb holes, various expectation values, and radial energy distributions (energy densities) are considered. It is shown that whilst the CS wavefunction can capture the behaviour of the wavefunction at the singularities of the Coulomb potential corresponding to the coalescence of two particles and decreases the area of the primary static Coulomb hole by nearly 30% compared to HF for He and Li++, it is unable to accurately model expectation values that depend on the whole of space and key features of the electron density behaviour in dynamic Coulomb holes and the energy density behaviour in energy distributions. These issues are amplified when considering the hydride ion and a system with the critical nuclear charge for binding. <br>

本数据集配套2022年11月发表于《Molecular Physics》的学术论文。压缩包包含7个子目录，分别存储：(i) 优化后的多体波函数；(ii) 静态库仑空穴数据（对应图3）；(iii) 动态库仑空穴数据（对应图4与图5）；(iv) “精确”电子关联能数据（对应图6）；(v) 以电子间坐标（intracule coordinate）r为自变量的能量密度数据（对应图7）；(vi) 以电子质心坐标（extracule coordinate）R为自变量的能量密度数据（对应图8）；(vii) 使用科莱-萨尔韦蒂（Colle and Salvetti, CS）与李-杨-帕（Lee-Yang-Parr, LYP）泛函计算得到的径向电子关联能分布数据（对应图9）。如需了解数据细节，请查阅压缩包内的Data_readme_notes文件。所有数据文件格式涵盖pd、sv、txt，均为纯文本格式，可通过任意文本编辑器打开。部分子目录中还附带了用于生成论文配图的LaTeX源文件（.tex格式），需借助LaTeX软件或编辑器编译生成。

摘要：本研究针对少电子体系的电子关联近似效应开展探究，采用三类多体波函数：全关联（FC）多体波函数、哈特利-福克（Hartree Fock, HF）波函数，以及常用于推导经典李-杨-帕（LYP）关联泛函的科莱-萨尔韦蒂雅斯特罗夫（Jastrow）型波函数（CS）。研究涵盖电子关联能、静态与动态库仑空穴、各类量子力学期望值，以及径向能量分布（能量密度）等内容。结果显示：尽管CS波函数能够准确捕捉两粒子重合时库仑势奇点处的波函数行为，且相较于HF波函数，可将氦（He）与二价锂离子（Li++）的主静态库仑空穴面积降低近30%，但该波函数无法精准建模依赖于全空间的期望值，也无法准确描述动态库仑空穴中的电子密度特征与能量分布的能量密度行为。在研究氢负离子（H⁻）以及具有临界结合核电荷的体系时，上述缺陷会被进一步放大。