单系镧原子的DFT计算：任务像看起来那么简单吗？

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-03-07 DOI:10.1016/j.comptc.2025.115170

Vladimir A. Basiuk

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引用次数: 0

摘要

我们测试了三种不受自旋约束的DFT计算方案（DMol3模块内具有DSPP和ECP伪势的PBE-D2/DNP理论水平，以及TURBOMOLE封装内的PBE-D2/def2-ECP），以验证其中一种方案能够成功地对全系列孤立镧系原子（La到Lu）进行单点计算，并比较了所获得的基本电子特性，如自旋值（即未配对电子的数量）、自旋密度图、HOMO-LUMO图、还有间隙能。在TURBOMOLE中发现了一些严重的问题(Tm和Lu无法计算；La， Eu和Tb的自旋值不切实际)，但在0.0001 Ha的目标热涂抹值下，从未检测到分数轨道占用。采用DMol3时，可以用DSPP完成全套；与ECP，结核除外。然而，在某些情况下，检测到分数轨道占用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

DFT calculations on single lanthanide atoms: Is the task as simple as it seems?

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DFT calculations on single lanthanide atoms: Is the task as simple as it seems?

We tested three spin-unconstrained DFT calculation schemes (PBE-D2/DNP theoretical level with DSPP and ECP pseudopotentials within DMol³ module, and PBE-D2/def2-ECP within TURBOMOLE package) to verify which of them allows for the successful single-point calculations on the full series of isolated lanthanide atoms (La to Lu), and compared the basic electronic characteristics obtained such as spin values (that is, the number of unpaired electrons), spin density plots, HOMO-LUMO plots, and the gap energies. A number of serious problems were found with TURBOMOLE (impossibility of calculations for Tm and Lu; unrealistic spin values for La, Eu and Tb), but a fractional orbital occupancy was never detected at the target thermal smearing value of 0.0001 Ha. When employing DMol³, the full set can be completed with DSPP; with ECP, with the exception of Tb. However, in some cases a fractional orbital occupancy was detected.

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.