ABSTRACT By means of comparing molar volumes at reference ambient conditions (298 K, 1.105 Pa) of 160 pressure-driven polymorphic transitions in chalcogenides, germanates, silicates, simple molecular compounds, elemental non-metals and a few metals it is shown that for reconstructive transitions between 0.1 and 150 GPa, mean volume contraction ranges around 11% for about 85% of all examined materials. The mean volume change is 7–9% for the first and second transition in trimorphic, and 4–5% for the third transition in tetramorphic systems. Less than 15% of the examined materials deviate systematically from these general correlations and follow a correlation ΔV ≈ 3·exp(ΔV’/15) (with ΔV the volume reduction upon the lower and ΔV’ upon the higher pressure transitions). These materials include metastable high pressure polymorphs from shock compression, materials with frustrated ordering, materials with macroscopic disorder like water-ices, and high-pressure electrides. Thus, the correlation of volumes that governs these phase transitions is independent on structure types but ruled by the configurational entropy of their ambient or intermediate structures.

中文翻译：

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压力引起的固态转变中体积变化的经验约束

摘要 通过比较参考环境条件 (298 K, 1.105 Pa) 下硫属化物、锗酸盐、硅酸盐、简单分子化合物、元素非金属和一些金属中 160 个压力驱动的多晶型转变的摩尔体积，表明对于重建在 0.1 到 150 GPa 之间的转变，对于大约 85% 的所有检查材料，平均体积收缩范围在 11% 左右。三态系统中第一次和第二次转变的平均体积变化为 7-9%，四态系统中的第三次转变为 4-5%。不到 15% 的检查材料系统地偏离了这些一般相关性，并遵循相关性 ΔV ≈ 3·exp(ΔV'/15)（ΔV 是较低的体积减少，而 ΔV' 是较高的压力转变）。这些材料包括来自冲击压缩的亚稳态高压多晶型物，具有失序有序的材料、具有宏观无序的材料（如水冰）和高压电化物。因此，控制这些相变的体积的相关性与结构类型无关，但受其环境或中间结构的构型熵控制。