Ariyarathna Isuru R
Physics and Chemistry of Materials (T-1), Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
Phys Chem Chem Phys. 2024 Aug 7;26(31):21099-21109. doi: 10.1039/d4cp01847h.
High-level electronic structure analysis of third-row transition metal (TM)-based diatomic species is challenging and has been perpetually lagging. In this work, fourteen and eighteen electronic states of HfN and HfN respectively are studied, employing multireference configuration interaction (MRCI) and coupled cluster singles doubles and perturbative triples [CCSD(T)] theories under larger correlation-consistent basis sets. Their potential energy curves (PECs), energetics, and spectroscopic parameters are reported. Core electron correlation effects on their properties are also investigated. Chemical bonding patterns of several low-lying electronic states are introduced based on the equilibrium electron configurations. The ground state of HfN (XΣ) has the 1σ2σ3σ1π electronic configuration, and the ionization of the 3σ electron produces the ground state of HfN (XΣ). Ground states of both HfN and HfN are triple bonded in nature and bear 124.86 and 109.10 kcal mol binding energies with respect to their ground state fragments. The findings of this work agree well with the limited experimental literature available and provide useful reference values for future experimental analysis of HfN and HfN.
基于第三周期过渡金属（TM）的双原子物种的高水平电子结构分析具有挑战性，并且一直滞后。在这项工作中，分别研究了HfN和HfN的14个和18个电子态，在更大的相关一致基组下采用多参考组态相互作用（MRCI）以及耦合簇单双激发和微扰三激发[CCSD(T)]理论。报告了它们的势能曲线（PEC）、能量学和光谱参数。还研究了核心电子相关效应对其性质的影响。基于平衡电子构型介绍了几种低能电子态的化学键模式。HfN（XΣ）的基态具有1σ2σ3σ1π电子构型，3σ电子的电离产生HfN（XΣ）的基态。HfN和HfN的基态本质上都是三键，相对于其基态片段分别具有124.86和109.10 kcal mol的结合能。这项工作的发现与现有的有限实验文献吻合良好，并为未来HfN和HfN的实验分析提供了有用的参考值。
