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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Role of Crystal Field in Mixed Alkali Metal Effect: Electron Paramagnetic Resonance Study of Mixed Alkali Metal Oxyfluoro Vanadate Glasses
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Role of Crystal Field in Mixed Alkali Metal Effect: Electron Paramagnetic Resonance Study of Mixed Alkali Metal Oxyfluoro Vanadate Glasses

机译：晶体场在混合碱金属效应中的作用：混合碱金属氧氟钒酸盐玻璃的电子顺磁共振研究

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摘要

The mixed alkali metal effect is a long-standing problem in glasses. Electron paramagnetic resonance (EPR) is used by several researchers to study the mixed alkali metal effect, but a detailed analysis of the nearest neighbor environment of the glass former using spin-Hamiltonian parameters was elusive. In this study we have prepared a series of vanadate glasses having general formula (mol %) 40 V_2O_5-30BaF_2-(30 ? x)LiF?xRbF with x = 5, 10, 15, 20, 25, and 30. Spin-Hamiltonian parameters of V~(4+) ions were extracted by simulating and fitting to the experimental spectra using EasySpin. From the analysis of these parameters it is observed that the replacement of lithium ions by rubidium ions follows a "preferential substitution model". Using this proposed model, we were able to account for the observed variation in the ratio of the g parameter, which goes through a maximum. This reflects an asymmetric to symmetric changeover of the alkali metal ion environment around the vanadium site. Further, this model also accounts for the variation in oxidation state of vanadium ion, which was confirmed from the variation in signal intensity of EPR spectra.
机译：混合碱金属效应是玻璃中长期存在的问题。几位研究人员使用电子顺磁共振（EPR）来研究混合碱金属效应，但是使用自旋哈密顿参数无法详细分析玻璃成型机的最邻近环境。在这项研究中，我们制备了一系列钒酸盐玻璃，它们的通式（摩尔％）为40 V_2O_5-30BaF_2-（30？x）LiF？xRbF，x = 5、10、15、20、25和30。自旋哈密顿量通过使用EasySpin模拟并拟合实验光谱来提取V〜（4+）离子的参数。从这些参数的分析可以看出，that离子置换锂离子遵循“优先置换模型”。使用这个建议的模型，我们能够解释g参数的比率所观察到的变化，该变化经历了最大值。这反映了钒位点周围碱金属离子环境的不对称转换。此外，该模型还考虑了钒离子氧化态的变化，这已从EPR光谱信号强度的变化得到了证实。

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