论文标题

核心依赖性特性的混合横梁高斯基础集:li-ne的sto-rg和sto-r2g

Mixed ramp-Gaussian basis sets for core-dependent properties: STO-RG and STO-R2G for Li-Ne

论文作者

Cox, Claudia S., Zapata, Juan Camilo, McKemmish, Laura K.

论文摘要

现代量子化学中使用的传统高斯基集缺乏电子核尖,因此难以准确描述核心电子性质。最近介绍的新型基集类型的混合横梁高斯人引入了一种新的原始功能,称为坡道功能,该功能解决了这个问题。本文介绍了三个新的混合横冲直撞 - 高斯基集合 - sto-r,sto-rg和sto-r2g,它们由斜坡和高斯原始函数的线性组合制成,这些函数是从单核 - zeta slater基集为ements elements li到ne的单核zeta slater基集得出的。这种推导与著名的sto-$ n $ g基套装相似。发现STO-RG基础函数的表现优于STO-3G基函数,而STO-R2G的表现优于STO-6G,无论是在波函数拟合和其他关键数量方面,例如单电子能和电子核CUSP。本文的第二部分对如何通过修改核心基础函数转换为标准的全高斯基础集进行了准备研究。使用碳的6-31G基集的测试案例,我们确定第二高斯原始原始词直接拟合ramp-gaussian核心基础功能直接适用于全高斯核心基础函数,而不是拟合在slater基础函数时。此外,我们确定了单核Zeta的基集,因此应该最直接地转换为将来的混合横梁基础基集。

The traditional Gaussian basis sets used in modern quantum chemistry lack an electron-nuclear cusp, and hence struggle to accurately describe core electron properties. A recently introduced novel type of basis set, mixed ramp-Gaussians, introduce a new primitive function called a ramp function which addresses this issue. This paper introduces three new mixed ramp-Gaussian basis sets - STO-R, STO-RG and STO-R2G, made from a linear combination of ramp and Gaussian primitive functions - which are derived from the single-core-zeta Slater basis sets for the elements Li to Ne. This derivation is done in an analogous fashion to the famous STO-$n$G basis sets. The STO-RG basis functions are found to outperform the STO-3G basis functions and STO-R2G outperforms STO-6G, both in terms of wavefunction fit and other key quantities such as the one-electron energy and the electron-nuclear cusp. The second part of this paper performs preparatory investigations into how standard all-Gaussian basis sets can be converted to ramp-Gaussian basis sets through modifying the core basis functions. Using a test case of the 6-31G basis set for carbon, we determined that the second Gaussian primitive is less important when fitting a ramp-Gaussian core basis function directly to an all-Gaussian core basis function than when fitting to a Slater basis function. Further, we identified the basis sets that are single-core-zeta and thus should be most straightforward to convert to mixed ramp-Gaussian basis sets in the future.

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