Martins L S C, Jorge F E, Franco M L, Ferreira I B
Departamento de Física, Universidade Federal do Espírito Santo, 29060-900 Vitória, Espírito Santo, Brazil.
J Chem Phys. 2016 Dec 28;145(24):244113. doi: 10.1063/1.4973377.
For the actinides, two segmented all-electron basis sets of valence double zeta quality plus polarization functions (DZP) are developed. One of them must be used along with the non-relativistic Hamiltonian, whereas the other with the Douglas-Kroll-Hess (DKH) one. Adding diffuse functions of s, p, d, f, and g symmetries to the non-relativistic and relativistic sets, augmented basis sets are developed. These functions are essential to describe correctly electrons far away from the nuclei. For some compounds, geometric parameters, atomic charges and valence orbital populations of the actinides, and bond dissociation energies are calculated using the Becke 3-parameter (exchange) and the Lee, Yang, and Parr (correlation) functional in conjunction with the DZP-DKH basis set. For Am and No, the static electric mean dipole polarizabilities are also reported. Comparison with benchmark theoretical and experimental values found in the literature is carried out. It is verified that the performances of the relativistic compact size basis sets generated in this work are regular, efficient, and reliable. They will be extremely helpful in molecular property calculations that need explicitly to consider the core electrons.
对于锕系元素，开发了两个价层双ζ质量加极化函数（DZP）的分段全电子基组。其中一个必须与非相对论哈密顿量一起使用，而另一个则与道格拉斯-克罗尔-赫斯（DKH）哈密顿量一起使用。通过向非相对论和相对论基组中添加s、p、d、f和g对称性的弥散函数，开发了增强基组。这些函数对于正确描述远离原子核的电子至关重要。对于一些化合物，使用Becke三参数（交换）和Lee、Yang和Parr（相关）泛函结合DZP-DKH基组计算了锕系元素的几何参数、原子电荷和价轨道布居以及键解离能。对于镅和锘，还报告了静态电平均偶极极化率。与文献中找到的基准理论值和实验值进行了比较。验证了本工作中生成的相对论紧凑尺寸基组的性能是规则、高效且可靠的。它们将对需要明确考虑内层电子的分子性质计算非常有帮助。
