Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA.
J Phys Chem B. 2023 Jun 8;127(22):5162-5168. doi: 10.1021/acs.jpcb.3c02089. Epub 2023 May 25.
We theoretically study the importance of many body correlations on the collective Debye-Waller (DW) factor in the context of the Nonlinear Langevin Equation (NLE) single-particle activated dynamics theory of glass transition and its extension to include collective elasticity (ECNLE theory). This microscopic force-based approach envisions structural alpha relaxation as a coupled local-nonlocal process involving correlated local cage and longer range collective barriers. The crucial question addressed here is the importance of the deGennes narrowing contribution versus a literal Vineyard approximation for the collective DW factor that enters the construction of the dynamic free energy in NLE theory. While the Vineyard-deGennes approach-based NLE theory and its ECNLE theory extension yields predictions that agree well with experimental and simulation results, use of a literal Vineyard approximation for the collective DW factor massively overpredicts the activated relaxation time. The current study suggests many particle correlations are crucial for a reliable description of activated dynamics theory of model hard sphere fluids.
我们从理论上研究了多体相关性对集体德拜-沃勒(DW)因子的重要性,这是玻璃化转变的非线性朗之万方程(NLE)单粒子激活动力学理论及其扩展到包括集体弹性(ECNLE 理论)的范畴。这种基于微观力的方法将结构α弛豫设想为一个涉及相关局部笼和更长程集体势垒的局部-非局部耦合过程。这里要解决的关键问题是德根内斯变窄贡献与进入 NLE 理论构建动态自由能的集体 DW 因子的文字 Vineyard 近似相比的重要性。虽然基于 Vineyard-deGennes 方法的 NLE 理论及其 ECNLE 理论扩展的预测与实验和模拟结果吻合良好,但对集体 DW 因子的文字 Vineyard 近似会极大地高估激活弛豫时间。目前的研究表明,多粒子相关性对于可靠描述模型硬球流体的激活动力学理论至关重要。