Department of Chemistry, Washington State University , Pullman, Washington 99164, United States.
J Phys Chem A. 2013 Nov 21;117(46):11874-80. doi: 10.1021/jp403078j. Epub 2013 May 24.
High-quality static electric dipole polarizabilities have been determined for the ground states of the hard-sphere cations of U, Np, and Pu in the III and IV oxidation states. The polarizabilities have been calculated using the numerical finite field technique in a four-component relativistic framework. Methods including Fock-space coupled cluster (FSCC) and Kramers-restricted configuration interaction (KRCI) have been performed in order to account for electron correlation effects. Comparisons between polarizabilities calculated using Dirac-Hartree-Fock (DHF), FSCC, and KRCI methods have been made using both triple- and quadruple-ζ basis sets for U(4+). In addition to the ground state, this study also reports the polarizability data for the first two excited states of U(3+/4+), Np(3+/4+), and Pu(3+/4+) ions at different levels of theory. The values reported in this work are the most accurate to date calculations for the dipole polarizabilities of the hard-sphere tri- and tetravalent actinide ions and may serve as reference values, aiding in the calculation of various electronic and response properties (for example, intermolecular forces, optical properties, etc.) relevant to the nuclear fuel cycle and material science applications.
已为 III 价和 IV 价的 U、Np 和 Pu 硬球阳离子的基态确定了高质量的静电偶极极化率。使用四分量相对论框架中的数值有限场技术计算了极化率。为了考虑电子相关效应，进行了包括 Fock 空间耦合簇 (FSCC) 和 Kramers 限制组态相互作用 (KRCI) 在内的方法。使用三 ζ 和四 ζ 基组对 U(4+)进行了使用 Dirac-Hartree-Fock (DHF)、FSCC 和 KRCI 方法计算的极化率之间的比较。除基态外，本研究还报告了不同理论水平下 U(3+/4+)、Np(3+/4+)和 Pu(3+/4+)离子的前两个激发态的极化率数据。本工作中报告的值是迄今为止硬球三价和四价锕系离子偶极极化率的最精确计算值，可作为参考值，有助于计算与核燃料循环和材料科学应用相关的各种电子和响应性质（例如，分子间力、光学性质等）。
