Institute for Theoretical Physics, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
Chemical and Biological Physics Department, Weizmann Institute of Science, Rehovot 7610001, Israel.
J Chem Phys. 2018 Jun 7;148(21):214502. doi: 10.1063/1.5024776.
Intrinsically generated structural disorder endows glassy materials with a broad distribution of various microscopic quantities-such as relaxation times and activation energies-without an obvious characteristic scale. At the same time, macroscopic glassy responses-such as Newtonian (linear) viscosity and nonlinear plastic deformation-are widely interpreted in terms of a characteristic energy scale, e.g., an effective temperature-dependent activation energy in Arrhenius relations. Nevertheless, despite its fundamental importance, such a characteristic energy scale has not been robustly identified. Inspired by the accumulated evidence regarding the crucial role played by disorder- and frustration-induced soft quasilocalized excitations in determining the properties and dynamics of glasses, we propose that the bulk average of the glass response to a localized force dipole defines such a characteristic energy scale. We show that this characteristic glassy energy scale features remarkable properties: (i) It increases dramatically in underlying inherent structures of equilibrium supercooled states approaching the glass transition temperature T, significantly surpassing the corresponding increase in the macroscopic shear modulus, dismissing the common view that structural variations in supercooled liquids upon vitrification are minute. (ii) Its variation with annealing and system size is very similar in magnitude and form to that of the energy of the softest non-phononic vibrational mode, thus establishing a nontrivial relation between a rare glassy fluctuation and a bulk average response. (iii) It exhibits striking dependence on spatial dimensionality and system size due to the long-ranged fields associated with quasilocalization, which are speculated to be related to peculiarities of the glass transition in two dimensions. In addition, we identify a truly static growing lengthscale associated with the characteristic glassy energy scale and discuss possible connections between the increase of this energy scale and the slowing down of dynamics near the glass transition temperature. Open questions and future directions are discussed.
固有产生的结构无序赋予玻璃态材料各种微观量的广泛分布,例如弛豫时间和激活能,而没有明显的特征尺度。同时,宏观玻璃态响应,如牛顿(线性)粘度和非线性塑性变形,广泛地用特征能量尺度来解释,例如 Arrhenius 关系中的有效温度依赖激活能。然而,尽管这种特征能量尺度具有重要意义,但它并没有被稳健地确定。受无序和挫折诱导的软准局域激发在确定玻璃性质和动力学方面的关键作用的积累证据的启发,我们提出,玻璃对局部力偶的体响应平均值定义了这种特征能量尺度。我们表明,这种特征玻璃能量尺度具有显著的性质:(i)它在接近玻璃化转变温度 T 的平衡过冷状态的基本结构中急剧增加,明显超过宏观剪切模量的相应增加,排除了在玻璃化过程中过冷液体结构变化微小的常见观点。(ii)它随退火和系统尺寸的变化与最软非声子振动模式的能量非常相似,从而在罕见的玻璃态涨落和体平均响应之间建立了一种非平凡的关系。(iii)由于与准局域化相关的远程场,它表现出显著的空间维度和系统尺寸依赖性,这被推测与二维玻璃转变的特殊性有关。此外,我们确定了与特征玻璃能量尺度相关的真正静态生长长度尺度,并讨论了这种能量尺度的增加与动力学在玻璃化转变温度附近减慢之间的可能联系。讨论了开放性问题和未来的方向。