为锂里德伯态的高精度从头算描述制备小型高斯基组
Preparing Small Gaussian Basis for Highly Accurate Ab Initio Description of Lithium Rydberg States
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中文总结 AI 辅助
本文开发新型小型高精度高斯基组，用于锂n=7及以下各类角动量对称性里德伯态的高精度从头算描述，其精度优于同类通用基组，为复杂体系的里德伯态研究奠定基础。
中文摘要 AI 辅助
本文开发了一种新型小型高精度高斯基组，用于锂（Li）n=7及以下、S、P、D、F、G角动量对称性的里德伯激发态的从头算描述，并给出了合适的优化方案。将所得里德伯激发能与其他高精度方法的结果对比，在EOM-CCSD理论水平下，该新基组的激发能和电离势精度高于10⁻² eV，且使用的基函数数量更少，结果优于同类通用高斯基组。一维里德伯轨道切面图显示，沿原子半径对数尺度呈现规则节点结构，延伸至距核数十埃处。所提出的里德伯基组生成方法，是推进更复杂体系（如重原子和多原子分子）的常规从头算里德伯态相关研究的重要一步。
英文摘要
A new small and highly accurate Gaussian basis set has been developed for the ab initio description of $^2$Li Rydberg excited states up to $n = 7$ and S, P, D, F, and G angular momentum symmetry, and the appropriate optimization protocol is presented. The obtained Rydberg excitation energies are compared with results from other highly accurate approaches. At the EOM-CCSD level of theory the new basis exhibits higher than $10^{-2}$ eV accuracy of the excitation energies and the ionization potential and provides superior results than an analogous universal Gaussian basis set, while utilizing even smaller number of basis functions. Plots of the 1-dimensional Rydberg-orbital cuts reveal a regular nodal structure along the logarithmic scale of the atomic radius reaching tens of angstrom far from the nucleus. The presented Rydberg basis set generation methodology is an important step towards routine ab initio Rydberg-state related investigations of more complex systems, such as large atoms and polyatomic molecules.
