Nath Santu, Sengupta Shiladitya
Department of Physics, Indian Institute of Technology Roorkee 247667, India.
Tata Institute of Fundamental Research, Hyderabad 500046, India.
J Chem Phys. 2024 Jul 21;161(3). doi: 10.1063/5.0174563.
It has been recognized of late that even amorphous, glass-forming materials in two dimensions (2D) are affected by Mermin-Wagner-type long wavelength thermal fluctuation, which is inconsequential in three dimensions (3D). We consider the question of whether the effect of spatial dimension on dynamics is only limited to such fluctuations or if the nature of glassy dynamics is intrinsically different in 2D. To address it, we study the relationship between dynamics and thermodynamics using the Adam-Gibbs (AG) relation and the random first order transition (RFOT) theory. Using two model glass-forming liquids, we find that even after removing the effect of long wavelength fluctuations, the AG relation breaks down in two dimensions. Next, we consider the effect of anharmonicity of vibrational entropy-a second factor that affects the thermodynamics but not dynamics. Using the potential energy landscape formalism, we explicitly compute the configurational entropy, both with and without the anharmonic correction. We show that even with both the corrections, the AG relation still breaks down in 2D. The extent of deviation from the AG relation crucially depends on the attractive vs repulsive nature of interparticle interactions, choice of representative timescale (diffusion coefficient vs α-relaxation time), and implies that the RFOT scaling exponents also depend on these factors. Thus, our results suggest that some differences in the nature of glassy dynamics between 2D and 3D remain that are not explained by long wavelength fluctuations.
最近人们已经认识到,即使是二维(2D)中的无定形玻璃形成材料也会受到Mermin-Wagner型长波长热涨落的影响,而这种涨落在三维(3D)中是无关紧要的。我们考虑空间维度对动力学的影响是否仅局限于此类涨落,或者二维中玻璃态动力学的本质是否内在不同。为了解决这个问题,我们使用亚当 - 吉布斯(AG)关系和随机一阶转变(RFOT)理论来研究动力学与热力学之间的关系。使用两种模型玻璃形成液体,我们发现即使去除长波长涨落的影响后,AG关系在二维中仍然不成立。接下来,我们考虑振动熵的非谐性的影响——这是另一个影响热力学但不影响动力学的因素。使用势能景观形式理论,我们明确计算了有无非谐修正时的构型熵。我们表明,即使进行了这两种修正,AG关系在二维中仍然不成立。与AG关系的偏离程度关键取决于粒子间相互作用的吸引与排斥性质、代表性时间尺度的选择(扩散系数与α弛豫时间),这意味着RFOT标度指数也取决于这些因素。因此,我们的结果表明,二维和三维中玻璃态动力学本质上的一些差异仍然存在,而这些差异无法用长波长涨落来解释。