Liu Xiao, Liu Da-Yong, Li Ting-Ting, Chen Dong-Meng, Zou Liang-Jian
Key Laboratory of Materials Physics, Institute of Solid State Physics, HFIPS, Chinese Academy of Science Hefei 230031 China
Science Island Branch of the Graduate School, University of Science and Technology of China Hefei 230026 China.
RSC Adv. 2021 Aug 25;11(46):28698-28703. doi: 10.1039/d1ra05578j. eCollection 2021 Aug 23.
Motivated by recent experimental observation [N. Z. Wang, , Inorg. Chem., 2019, , 9897], we investigated the electronic properties and chemical bonding in layered nitride-halide compounds ThNF and ThNCl using first-principles calculations to illustrate the interlayer interaction. The energy gaps and chemical valences of both compounds are in agreement with experimental data. The crystal orbital Hamiltonian population (COHP) and charge density differential analysis show that interlayer chemical bonding plays a more important role than that van der Waals interactions in ThNF and ThNCl, in contrast to isostructural ZrNCl and HfNCl. These results explain why it is difficult to intercalate ThNF and ThNCl with charged particles, as observed in experiments.
受近期实验观察结果[N. Z. Wang, , Inorg. Chem., 2019, , 9897]的启发，我们使用第一性原理计算研究了层状氮化物卤化物化合物ThNF和ThNCl中的电子性质和化学键，以阐明层间相互作用。两种化合物的能隙和化学价与实验数据一致。晶体轨道哈密顿布居（COHP）和电荷密度差分分析表明，与同结构的ZrNCl和HfNCl相比，层间化学键在ThNF和ThNCl中比范德华相互作用起更重要的作用。这些结果解释了为什么如实验中所观察到的那样，用带电粒子插入ThNF和ThNCl是困难的。
