期刊
CHEMISTRY OF MATERIALS
卷 26, 期 8, 页码 2617-2623出版社
AMER CHEMICAL SOC
DOI: 10.1021/cm5000999
关键词
-
资金
- HPC-EUROPA2 project [1212]
- European Commission Capacities Area, Research Infrastructures Initiative
- Austrian Science Fund (FWF) [P25702]
- Austrian Federal Ministry of Economy, Family and Youth
- Austrian National Foundation for Research, Technology, and Development
- Austrian Science Fund (FWF) [P25702] Funding Source: Austrian Science Fund (FWF)
We investigate theoretically the site occupancy of Al3+ in the fast-ion-conducting cubic-garnet Li7-3xAlx3+La3Zr2O12 (Ia-3d) using density functional theory. By comparing calculated and measured Al-27 NMR chemical shifts an analysis shows that Al3+ prefers the tetrahedrally coordinated 24d site and a distorted 4-fold coordinated 96h site. The site energies for Al3+ ions, which are slightly displaced from the exact crystallographic sites (i.e., 24d and 96h), are similar leading to a distribution of slightly different local oxygen coordination environments. Thus, broad Al-27 NMR resonances result reflecting the distribution of different isotropic chemical shifts and quadrupole coupling constants. From an energetic point of view, there is evidence that Al3+ could also occupy the 48g site with its almost regular octahedral coordination sphere. Although this has been reported by neutron powder diffraction, the NMR chemical shift calculated for such an Al3+ site has not been observed experimentally.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据