论文标题
一单电子离子的极化高斯基集
Polarized Gaussian basis sets from one-electron ions
论文作者
论文摘要
我们证明，可以从[1，z] $的$ y \ in [1，z] $的$ y \ y \ y \ y y \ y y \ y \ y \ y \ y \ y \ y \ y \ y \ y \ y \ y \ y \ y \ y \ y \ $ y \ $ y \ $ y \ y \ y \ y的简单准确性考虑可以从[1，z] $中获得的简单准确性考虑获得，因此根本不需要自符合的场计算。结果表明，具有常用通用高斯基集（UGB）的参数的脾气暴躁的基集[E. E. V. R. De Castro和F. E. Jorge，J。Chem。物理。 108，5225（1998）]再现了非相关的旋转旋转的球形hartree hartree-fock总能量，从完全数值计算到比UGB的准确性更高，这证明对某些元素显示出巨大的误差，例如。 0.19 $ e_ {h} $ th $^+$和0.13 $ e_ {h} $ for lu已针对单个原子配置进行了参数化。在显示了单电子方法的可行性之后，通过优化$ z^{（Z-1）+} $的均匀参数，为元素性表中的所有原子（$ 1 \ leq z \ leq118 $）形成部分能量优化的基集。由于本工作中建议的氢气高斯基集是严格由第一原则构建的，因此与以前的方法相比，也可以以相同的方式获得极化壳。与完全数值的参考值相比，通过对一小部分分子的计算来证明了极化基集的精度，即使对于诸如SF $ _6 $之类的具有挑战性的情况，这些参考值也可以达到化学精度。目前的方法直接扩展到相对论计算，并且可以促进既定表周期表之外的研究。
We demonstrate that basis sets suitable for electronic structure calculations can be obtained from simple accuracy considerations for the hydrogenic one-electron ions $Y^{(Y-1)+}$ for $Y\in[1,Z]$, necessitating no self-consistent field calculations at all. It is shown that even-tempered basis sets with parameters from the commonly-used universal Gaussian basis set (UGBS) [E. V. R. de Castro and F. E. Jorge, J. Chem. Phys. 108, 5225 (1998)] reproduce non-relativistic spin-restricted spherical Hartree-Fock total energies from fully numerical calculations to better accuracy than UGBS, which is shown to exhibit huge errors for some elements, e.g. 0.19 $E_{h}$ for Th$^+$ and 0.13 $E_{h}$ for Lu as it has been parametrized for a single atomic configuration. Having shown the feasibility of the one-electron approach, partially energy-optimized basis sets are formed for all atoms in the periodic table, $1\leq Z\leq118$, by optimizing the even-tempered parameters for $Z^{(Z-1)+}$. As the hydrogenic Gaussian basis sets suggested in the present work are built strictly from first principles, also polarization shells can be obtained in the same fashion in contrast to previous approaches. The accuracy of the polarized basis sets is demonstrated by calculations on a small set of molecules by comparison to fully numerical reference values, which show that chemical accuracy can be reached even for challenging cases like SF$_6$. The present approach is straightforward to extend to relativistic calculations, and could facilitate studies beyond the established periodic table.
