Department of Chemistry, Michigan State University, East Lansing, Michigan48824, United States.
J Phys Chem A. 2023 Jan 12;127(1):107-121. doi: 10.1021/acs.jpca.2c06968. Epub 2023 Jan 3.
Complete active space self-consistent field (CASSCF) and multireference configuration interaction with Davidson correction (MRCI+Q) calculations have been carried out for lawrencium fluoride (LrF) and lawrencium oxide (LrO) molecules, detailing 19 and 20 electronic states for LrF and LrO, respectively. For LrF, two dissociation channels were considered, Lr(P)+F(P) and Lr(D)+F(P). However, due to the more complex electronic manifold of LrO, three dissociation channels were computed: Lr(P)+O(P), Lr(D)+O(P), and Lr(P)+O(D). In addition, equilibrium bond lengths, harmonic vibrational frequencies ω, anharmonicity constants ωχ, Δ values, and excitation energies for the ground and several excited electronic states were calculated for both molecules, for the first time. Bond dissociation energies (BDEs) were calculated for LrF and LrO using several different levels of theory: unrestricted coupled-cluster with single, double, and perturbative triple excitations (UCCSD(T)), density functional theory (B3LYP, TPSS, M06-L, and PBE), and the correlation-consistent composite approach developed for -elements (-ccCA).
已针对镥氟（LrF）和镥氧化物（LrO）分子进行了完全活性空间自洽场（CASSCF）和多参考组态相互作用与戴维森修正（MRCI+Q）计算，分别详细描述了 LrF 和 LrO 的 19 个和 20 个电子态。对于 LrF，考虑了两个离解通道，Lr（P）+F（P）和 Lr（D）+F（P）。然而，由于 LrO 的电子态更为复杂，计算了三个离解通道：Lr（P）+O（P）、Lr（D）+O（P）和 Lr（P）+O（D）。此外，首次针对这两种分子计算了基态和几个激发态的平衡键长、简谐振动频率ω、非谐常数ωχ、Δ 值和激发能。使用多种不同理论水平（未受限制的耦合簇单、双和微扰三激发（UCCSD（T））、密度泛函理论（B3LYP、TPSS、M06-L 和 PBE）以及为-元素开发的相关一致复合方法（-ccCA））计算了 LrF 和 LrO 的键离解能（BDE）。
