Lu Jun-Bo, Cantu David C, Xu Cong-Qiao, Nguyen Manh-Thuong, Hu Han-Shi, Glezakou Vassiliki-Alexandra, Rousseau Roger, Li Jun
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084, China.
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
J Chem Theory Comput. 2021 Jun 8;17(6):3360-3371. doi: 10.1021/acs.jctc.1c00026. Epub 2021 May 25.
We have developed a new set of norm-conserving pseudopotentials and companion Gaussian basis sets for the actinide (An) series (Ac-Lr) using the Goedecker, Teter, and Hutter (GTH) formalism with the Perdew, Burke, and Ernzerhof (PBE) exchange-correlation functional of generalized gradient approximation. To test the accuracy and reliability of the newly parameterized An-GTH pseudopotentials and basis sets, a variety of benchmarks on actinide-containing molecules were carried out and compared to all-electron and available experimental results. The new pseudopotentials include both medium- ([Xe]4f) and large-core ([Xe]4f5d) options that successfully reproduce the structures and energetics, particularly redox processes. The medium-core size set, in particular, reproduces all-electron calculations over multiple oxidation states from 0 to VII, whereas the large-core set is suitable only for the early series elements and low oxidation states. The underlying reason for these transferability issues is discussed in detail. This work fills a critical void in the literature for studying the chemistry of 5f-block elements in the condensed phase.
我们使用戈德克、泰特和胡特（GTH）形式体系以及广义梯度近似的佩德韦、伯克和恩泽霍夫（PBE）交换关联泛函，为锕系（An）元素（Ac-Lr）开发了一套新的守恒规范赝势和配套的高斯基组。为了测试新参数化的An-GTH赝势和基组的准确性和可靠性，我们对含锕系元素的分子进行了各种基准测试，并与全电子计算结果和现有实验结果进行了比较。新的赝势包括中核（[Xe]4f）和大核（[Xe]4f5d）两种选项，它们成功地再现了结构和能量，特别是氧化还原过程。特别是中核尺寸集，在0到VII的多个氧化态下再现了全电子计算结果，而大核集仅适用于早期系列元素和低氧化态。我们详细讨论了这些可转移性问题的根本原因。这项工作填补了文献中研究凝聚相中5f族元素化学的关键空白。
