Baranau Vasili, Tallarek Ulrich
Department of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany.
Soft Matter. 2014 Oct 21;10(39):7838-48. doi: 10.1039/c4sm01439a. Epub 2014 Aug 26.
We computer-generated monodisperse and polydisperse frictionless hard-sphere packings of 10(4) particles with log-normal particle diameter distributions in a wide range of packing densities φ (for monodisperse packings φ = 0.46-0.72). We equilibrated these packings and searched for their inherent structures, which for hard spheres we refer to as closest jammed configurations. We found that the closest jamming densities φ(J) for equilibrated packings with initial densities φ ≤ 0.52 are located near the random close packing limit φ(RCP); the available phase space is dominated by basins of attraction that we associate with liquid. φ(RCP) depends on the polydispersity and is ∼ 0.64 for monodisperse packings. For φ > 0.52, φ(J) increases with φ; the available phase space is dominated by basins of attraction that we associate with glass. When φ reaches the ideal glass transition density φ(g), φ(J) reaches the ideal glass density (the glass close packing limit) φ(GCP), so that the available phase space is dominated at φ(g) by the basin of attraction of the ideal glass. For packings with sphere diameter standard deviation σ = 0.1, φ(GCP) ≈ 0.655 and φ(g) ≈ 0.59. For monodisperse and slightly polydisperse packings, crystallization is superimposed on these processes: it starts at the melting transition density φ(m) and ends at the crystallization offset density φ(off). For monodisperse packings, φ(m) ≈ 0.54 and φ(off) ≈ 0.61. We verified that the results for polydisperse packings are independent of the generation protocol for φ ≤ φ(g).
我们通过计算机生成了10⁴个粒子的单分散和多分散无摩擦硬球堆积,这些粒子具有对数正态粒径分布,处于广泛的堆积密度φ范围内(对于单分散堆积,φ = 0.46 - 0.72)。我们使这些堆积达到平衡并寻找它们的固有结构,对于硬球,我们将其称为最紧密堵塞构型。我们发现,初始密度φ≤0.52的平衡堆积的最紧密堵塞密度φ(J)位于随机密堆积极限φ(RCP)附近;可用相空间由我们认为与液体相关的吸引盆主导。φ(RCP)取决于多分散性,对于单分散堆积约为0.64。对于φ>0.52,φ(J)随φ增加;可用相空间由我们认为与玻璃相关的吸引盆主导。当φ达到理想玻璃化转变密度φ(g)时,φ(J)达到理想玻璃密度(玻璃密堆积极限)φ(GCP),因此在φ(g)时可用相空间由理想玻璃的吸引盆主导。对于球体直径标准差σ = 0.1的堆积,φ(GCP)≈0.655且φ(g)≈0.59。对于单分散和轻微多分散堆积,结晶叠加在这些过程之上:它从熔化转变密度φ(m)开始,在结晶偏移密度φ(off)结束。对于单分散堆积,φ(m)≈0.54且φ(off)≈0.61。我们验证了对于多分散堆积,在φ≤φ(g)时结果与生成协议无关。