Institut für Chemie, Universität Rostock, 18059 Rostock, Germany.
J Chem Phys. 2017 Jul 21;147(3):034304. doi: 10.1063/1.4994267.
A new ab initio interatomic potential energy curve for two ground-state xenon atoms is presented. It is based on supermolecular calculations at the coupled-cluster level with single, double, and perturbative triple excitations [CCSD(T)] employing basis sets up to sextuple-zeta quality, which were developed as part of this work. In addition, corrections were determined for higher coupled-cluster levels up to CCSDTQ as well as for scalar and spin-orbit relativistic effects at the CCSD(T) level. A physically motivated analytical function was fitted to the calculated interaction energies and used to compute the vibrational spectrum of the dimer, the second virial coefficient, and the dilute gas transport properties. The agreement with the best available experimental data for the investigated properties is excellent; the new potential function is superior not only to previous ab initio potentials but also to the most popular empirical ones.
提出了一个新的双氙基态原子的从头算原子间相互作用势能曲线。它是基于在耦合簇水平上的超分子计算，采用单、双和微扰三激发[CCSD(T)]，使用本工作中开发的基础集高达六重 zeta 质量。此外，还确定了更高的耦合簇水平（CCSDTQ）以及 CCSD(T)水平的标量和自旋轨道相对论效应的修正。将计算得到的相互作用能拟合到一个物理上合理的解析函数中，用于计算二聚体的振动光谱、第二维里系数和稀气体输运性质。与所研究性质的最佳现有实验数据的一致性非常好；新的势能函数不仅优于以前的从头算势能，而且也优于最流行的经验势能。
