Anionic order in Pb2Ti4O9F2 Revisited by nuclear magnetic resonance and density functional theory
Anionic order in Pb2Ti4O9F2 Revisited by nuclear magnetic resonance and density functional theory
复制标题
通过核磁共振和密度泛函理论重新审视 Pb2Ti4O9F2 中的阴离子顺序
DOI：
10.1039/d2dt00839d
复制
发表时间：
2022
影响因子：
4
通讯作者：
Reboredo Fernando A.
中科院分区：
文献类型：
--
作者：
Oka Kengo;Ichibha Tom;Kato Daichi;Noda Yasuto;Tominaga Yusuke;Yamada Kosei;Iwasaki Mitsunobu;Noma Naoki;Hongo Kenta;Maezono Ryo;Reboredo Fernando A.
用19F魔角自旋(MAS)、核磁共振(NMR)和密度泛函理论(DFT)相结合的方法研究了Pb2Ti4O9F2中F原子的有序性。这一分析表明，F原子主要占据了六个可用的不同位置中的两个，比率为73 ： 27。基于密度泛函理论的计算解释了F在这些位置上的占有率的偏好，并定量地再现了实验的占有率，与官能团的选择无关。我们得出结论，铅原子的6s2孤子对可能起到了一定的作用(∼为0.1eV/F.U)。在用偏态密度和晶体轨道哈密顿布居分析确定大多数和少数F占位时，将哈密顿布居分析应用于DFT波函数。
A combination of 19F magic angle spinning (MAS) nuclear magnetic resonance (NMR) and density functional theory (DFT) were used to study the ordering of F atoms in Pb2Ti4O9F2. This analysis revealed that F atoms predominantly occupy two of the six available inequivalent sites in a ratio of 73 : 27. DFT-based calculations explained the preference of F occupation on these sites and quantitatively reproduced the experimental occupation ratio, independent of the choice of functional. We concluded that the Pb atom's 6s2 lone pair may play a role (∼0.1 eV per f.u.) in determining the majority and minority F occupation sites with partial density of states and crystal orbital Hamiltonian population analyses applied to the DFT wave functions.