Mutneja Anoop, Schweizer Kenneth S
Department of Materials Science, University of Illinois, Urbana, Illinois, 61801, USA.
Department of Materials Research Laboratory, University of Illinois, Urbana, Illinois, 61801, USA.
Soft Matter. 2024 Sep 18;20(36):7284-7299. doi: 10.1039/d4sm00693c.
We apply the hybrid projectionless dynamic theory (hybrid PDT) formulation of the elastically collective nonlinear Langevin equation (ECNLE) activated dynamics approach to study dense fluids of sticky spheres interacting with short range attractions. Of special interest is the problem of non-monotonic evolution with short range attraction strength of the elastic modulus ("re-entrancy") at very high packing fractions far beyond the ideal mode coupling theory (MCT) nonergodicity boundary. The dynamic force constraints explicitly treat the bare attractive forces that drive transient physical bond formation, while a projection approximation is employed for the singular hard-sphere potential. The resultant interference between repulsive and attractive forces contribution to the dynamic vertex results in the prediction of localization length and elastic modulus re-entrancy, qualitatively consistent with experiments. The non-monotonic evolution of the structural (alpha) relaxation time predicted by the ECNLE theory with the hybrid PDT approach is explored in depth as a function of packing fraction, attraction strength, and attraction range. Isochronal dynamic arrest boundaries based on activated relaxation display the classic non-monotonic glass melting form. Comparisons of these results with the corresponding predictions of ideal MCT, and also the ECNLE and NLE activated theories based on projection, reveal large qualitative differences. The consequences of stochastic trajectory fluctuations on intra-cage single particle dynamics with variable strength of attractions are also studied. Large dynamical heterogeneity effects in attractive glasses are properly captured. These include a rapidly increasing amplitude of the non-Gaussian parameter with packing fraction and a non-monotonic evolution with attraction strength, in qualitative accord with recent simulations. Extension of the microscopic theoretical approach to treat double yielding in attractive glass nonlinear rheology is possible.
我们应用弹性集体非线性朗之万方程(ECNLE)激活动力学方法的混合无投影动态理论(混合PDT)公式,来研究具有短程吸引力的粘性球体致密流体。特别令人感兴趣的是,在远高于理想模式耦合理论(MCT)非遍历性边界的非常高的填充分数下,弹性模量随短程吸引力强度的非单调演化问题(“再入”)。动态力约束明确处理驱动瞬态物理键形成的裸吸引力,而对奇异硬球势采用投影近似。排斥力和吸引力对动态顶点贡献之间的干扰,导致了对定位长度和弹性模量再入的预测,与实验定性一致。深入探讨了用混合PDT方法由ECNLE理论预测的结构(α)弛豫时间随填充分数、吸引力强度和吸引力范围的非单调演化。基于激活弛豫的等时动态停滞边界呈现出经典的非单调玻璃熔化形式。将这些结果与理想MCT的相应预测,以及基于投影的ECNLE和NLE激活理论进行比较,揭示了很大的定性差异。还研究了具有可变吸引力强度的笼内单粒子动力学中随机轨迹波动的影响。吸引力玻璃中的大动力学非均匀性效应得到了恰当捕捉。这些效应包括非高斯参数的幅度随填充分数迅速增加,以及随吸引力强度的非单调演化,这与最近的模拟定性一致。将微观理论方法扩展到处理吸引力玻璃非线性流变学中的双屈服是可能的。