Mulliken Center for Theoretical Chemistry, Clausius-Institute of Physical and Theoretical Chemistry, University of Bonn, Bonn, Germany.
J Comput Chem. 2023 Jun 5;44(15):1418-1425. doi: 10.1002/jcc.27097. Epub 2023 Mar 11.
Consistent basis sets of triple-zeta valence quality for the elements La-Lu were derived for periodic quantum-chemical solid-state calculations. They are an extension of the pob-TZVP-rev2 [D. Vilela Oliveira, et al., J. Comput. Chem. 2019, 40(27), 2364-2376], [J. Laun and T. Bredow, J. Comput. Chem. 2021, 42(15), 1064-1072], [J. Laun and T. Bredow, J. Comput. Chem. 2022, 43(12), 839-846] basis sets and are based on the fully relativistic effective core potentials of the Stuttgart/Cologne group and on the def2-TZVP valence basis of the Ahlrichs group. The basis sets are constructed to minimize the basis set superposition error in crystalline systems. The contraction scheme, orbital exponents, and contraction coefficients were optimized in order to ensure robust and stable self-consistent-field convergence for a set of compounds and metals. For the applied PW1PW hybrid functional, the average deviations of the calculated lattice constants from experimental references are smaller with pob-TZV-rev2 than with standard basis sets available from the CRYSTAL basis set database. After augmentation with single diffuse s- and p-functions, reference plane-wave band structures of metals can be accurately reproduced.
为了进行周期性量子化学固态计算，我们为镧系元素（La-Lu）推导出了一套基于完全相对论有效核势和 Ahlrichs 集团 def2-TZVP 价基的三 ζ 价质量的一致基础集。该基础集是对基于 Vilela Oliveira 等人的 pob-TZVP-rev2 [D. Vilela Oliveira, et al., J. Comput. Chem. 2019, 40(27), 2364-2376]，[J. Laun 和 T. Bredow, J. Comput. Chem. 2021, 42(15), 1064-1072]，[J. Laun 和 T. Bredow, J. Comput. Chem. 2022, 43(12), 839-846]基础集的扩展。该基础集的构造旨在最小化晶体系统中的基组叠加误差。为了确保一组化合物和金属的自洽场收敛稳定，我们对收缩方案、轨道指数和收缩系数进行了优化。对于应用的 PW1PW 混合泛函，与 CRYSTAL 基组数据库中可用的标准基组相比，pob-TZV-rev2 计算出的晶格常数与实验参考值的平均偏差更小。经过单个弥散 s 和 p 函数的扩充，可以准确地再现金属的参考平面波能带结构。
