Aebersold Lucas E, Wilson Angela K
Department of Chemistry, Michigan State University, East Lansing, Michigan 48824-1322, United States.
J Phys Chem A. 2021 Aug 19;125(32):7029-7037. doi: 10.1021/acs.jpca.1c06155. Epub 2021 Aug 9.
The importance of spin-orbit effects on the predictions of energetic properties of actinide compounds has been considered for 18 different density functionals, comparing the spin-orbit and non-spin-orbit ("standard") forms of density functional theory (DFT). A set of enthalpies of formation for 66 small actinide (Th-Am) compounds-the An66 set, for which experimental data are available-have been investigated. The set includes actinide halides, oxides, and oxohalides in the general form AnOX, where = 0-6, = 0-3, and X = F, Cl, Br, or I. The impact of basis set choice was investigated, and to help account for the impact of relativity, the Stuttgart general and segmented contracted atomic natural orbital (ANO) basis sets paired with small core relativistic effective core potentials (RECP) as well as all-electron calculations utilizing the third-order Douglas-Kroll-Hess were considered.
针对18种不同的密度泛函，通过比较密度泛函理论（DFT）的自旋轨道和非自旋轨道（“标准”）形式，研究了自旋轨道效应对于锕系化合物能量性质预测的重要性。对66种小的锕系（Th-Am）化合物（即An66集合，有相关实验数据）的一组生成焓进行了研究。该集合包括通式为AnOX的锕系卤化物、氧化物和卤氧化物，其中 = 0 - 6， = 0 - 3，且X = F、Cl、Br或I。研究了基组选择的影响，为了有助于解释相对论效应的影响，考虑了与小核相对论有效核势（RECP）配对的斯图加特通用和分段收缩原子自然轨道（ANO）基组，以及利用三阶道格拉斯 - 克罗尔 - 赫斯方法进行的全电子计算。
