论文标题

固体与液体样在超级离子Cu2x(X = S,SE)中的液体样行为:无弹性中子散射和AB-Initio分子动力学研究

Solid-like to Liquid-like Behavior of Cu Diffusion in Superionic Cu2X (X=S, Se): An Inelastic Neutron Scattering and Ab-Initio Molecular Dynamics Investigation

论文作者

Kumar, Sajan, Gupta, M. K., Goel, Prabhatasree, Mittal, R., Delaire, Olivier, Thamizhavel, A., Rols, S., Chaplot, S. L.

论文摘要

CU2SE和CU2是具有较大扩散系数的超级离子导体的出色模型系统,据报道表现出不同的固液样Cu-ion扩散。在本文中,我们用依赖温度的AB-Initio分子动力学(AIMD)模拟和非弹性中子散射(INS)实验来阐明这些化合物的原子动力学。使用动力学结构因子和范夫相关函数,我们询问跳跃时间,跳高长度分布和相关的扩散系数。在500 K处的立方cu2se中,我们发现固体样扩散,cu-phump长度与晶体中的首次邻居Cu-Cu距离匹配〜3Å,并且明确定义了涉及Cu振动的光子声子。高于700 K,跳长分布变成了宽大的最大捕捞,跨越了4Å,跨越了第一和第二个邻居晶格距离,并同时扩大了状态的Cu-Phonon密度。此外,在900 K以上,Cu扩散变得接近液体状,铜原子的分布不断连接晶体位点,而涉及Cu运动的振动模式被高度阻尼,尽管仍然没有像液体中那样完全阻尼。在低温下,固体样扩散与先前的X射线衍射和准中子散射实验一致,而对液体样扩散的高温观察与以前的AIMD模拟一致。我们还报告了六角形和立方超级离子相的CU2中的AIMD模拟,并分别在低温和​​高温下观察到相似的固体和液体样扩散。计算出的离子传导性与报告的实验值一致。

Cu2Se and Cu2S are excellent model systems of superionic conductors with large diffusion coefficients that have been reported to exhibit different solid-liquid-like Cu-ion diffusion. In this paper, we clarify the atomic dynamics of these compounds with temperature-dependent ab-initio molecular dynamics (AIMD) simulations and inelastic neutron scattering (INS) experiments. Using the dynamical structure factor and Van-Hove correlation function, we interrogate the jump-time, hopping length distribution and associated diffusion coefficients. In cubic-Cu2Se at 500 K, we find solid-like diffusion with Cu-jump lengths matching well the first-neighbour Cu-Cu distance of ~3 Å in the crystal, and clearly defined optic phonons involving Cu-vibrations. Above 700 K, the jump-length distribution becomes a broad maximum cantered around 4 Å, spanning the first and second neighbour lattice distances, and a concurrent broadening of the Cu-phonon density of states. Further, above 900 K, the Cu-diffusion becomes close to liquid-like, with distributions of Cu-atoms continuously connecting crystal sites, while the vibrational modes involving Cu motions are highly damped, though still not fully over-damped as in a liquid. At low temperatures, the solid-like diffusion is consistent with previous X-ray diffraction and quasielastic neutron scattering experiments, while the higher-temperature observation of the liquid-like diffusion is in agreement with previous AIMD simulations. We also report AIMD simulations in Cu2S in the hexagonal and cubic superionic phases, and observe similar solid and liquid-like diffusion at low- and high-temperatures, respectively. The calculated ionic-conductivity is in fair agreement with reported experimental values.

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