Institut für Festkörperphysik, Technische Universität Darmstadt, Hochschulstr. 6, 64289 Darmstadt, Germany.
J Chem Phys. 2017 Jul 21;147(3):034505. doi: 10.1063/1.4993445.
We perform molecular dynamics simulations to ascertain effects of the molecular polarity on structural and dynamical properties of water-like systems, in particular, on their glassy slowdown. To systematically vary the molecular dipole moments, we scale the partial charges of the established SPC/E and TIP4P/2005 models. In broad ranges of the molecular polarity, the studied SPC/E and TIP4P/2005 descendants show a density anomaly, which can be attributed to the removal of water molecules interstitial between the first and the second neighbor shells upon cooling. While all considered modified water models behave as typical glass formers, the structural relaxation time τ heavily depends on the molecular dipole moment. This large dynamical diversity is exploited to systematically ascertain characteristic properties of glass-forming liquids. For all studied water-like systems, we observe a close relation between the activation energy E describing the Arrhenius behavior of the regular liquid and the glass transition temperature T characterizing the supercooled liquid, explicitly, E/T≈10. Moreover, decomposing the activation energy of the structural relaxation according to E(T)=E+E(T), we show that the glassy slowdown of all modified water molecules can fully be traced back to an exponential temperature dependence of the contribution E(T) related to cooperative dynamics. Extrapolation of this behavior suggests a common value at the glass transition temperature, E(T)/T≈25. Finally, we discuss links between the structural relaxation and the vibrational displacement, as proposed in various theoretical approaches to the glass transition.
我们进行分子动力学模拟,以确定分子极性对类水体系结构和动力学性质的影响,特别是对其玻璃化减速的影响。为了系统地改变分子偶极矩,我们对已建立的 SPC/E 和 TIP4P/2005 模型的部分电荷进行缩放。在分子极性的广泛范围内,研究的 SPC/E 和 TIP4P/2005 衍生模型表现出密度异常,这可以归因于冷却过程中去除了处于第一和第二近邻壳之间的水分子。虽然所有考虑的改性水模型都表现为典型的玻璃形成体,但结构弛豫时间 τ 严重依赖于分子偶极矩。这种大的动力学多样性被利用来系统地确定玻璃形成液体的特征性质。对于所有研究的类水体系,我们观察到描述规则液体 Arrhenius 行为的激活能 E 与描述过冷液体的玻璃化转变温度 T 之间存在密切关系,具体来说,E/T≈10。此外,根据 E(T)=E+E(T) 分解结构弛豫的激活能,我们表明所有改性水分子的玻璃化减速都可以完全归因于与协同动力学相关的贡献 E(T) 的指数温度依赖性。这种行为的外推表明在玻璃转变温度处存在共同值,E(T)/T≈25。最后,我们讨论了结构弛豫与振动位移之间的联系,这是各种玻璃转变理论方法中提出的。