论文标题

对TERT丁醇溶液的最大密度的最高密度进行建模

Modeling the temperature of maximum density of aqueous tert-butanol solutions

论文作者

Marques, Murilo S., Lomba, Enrique, Noya, Eva G., González-Salgado, D., Barbosa, Marcia C.

论文摘要

高稀释时的短链醇是增强水的异常行为的极少数溶质之一,尤其是最大密度温度的值。这种特殊的特征是在六十年代初在实验中首次发现的,就原子模型而言,完全无法解释。在本文中,我们首先引入了TERT叔丁醇的两个站点模型,其中涉及氢键的相互作用由Stillinger-Weber电位表示,这是在Molinero和Moore首次引入的思想之后[J. [J.物理。化学B,113,4008,(2009)]。我们的模型参数很适合,以便半优化地重现先前提出的联合原子和所有原子OPLS模型的实验密度和蒸发焓。使用Molinero和Moore引入的上述潜在模型表示水,并且优化了水与Tert丁醇之间的交叉相互作用参数,以在混合物的整个组成范围内对实验过量的焓和体积进行合理的描述。我们将看到,我们的简单模型能够在非常低的酒精摩尔分数的最高密度变化中重现最大值的存在,然后大大降低,直到密度异常本身消失为止。我们将这种行为与水的局部结构变化相关联,并将其与水/丁醇混合物的全部原子模拟的结果进行了比较。

Short-chain alcohols at high dilution are among the very few solutes that enhance the anomalous behavior of water, in particular the value of the temperature of maximum density. This peculiar feature, first discovered experimentally in the early sixties, has remained elusive to a full explanation in terms of atomistic models. In this paper, we first introduce a two-site model of tert-butanol in which the interactions involving hydrogen bonding are represented by a Stillinger-Weber potential, following the ideas first introduced by Molinero and Moore, [J. Phys. Chem. B, 113, 4008, (2009)]. Our model parameters are fit so as to semi-quantitatively reproduce the experimental densities and vaporization enthalpies of previously proposed united atom and all atom OPLS models. Water is represented using the aforementioned potential model introduced by Molinero and Moore, with cross interaction parameters between water and tert-butanol optimized to yield a reasonable description of the experimental excess enthalpies and volumes over the whole composition range of the mixture. We will see that our simple model is able to reproduce the presence of a maximum in the change of the temperature of maximum density for very low alcohol mole fractions, followed by a considerable decrease until the density anomaly itself disappears. We have correlated this behavior with changes in the local structure of water and compared it with the results of all-atom simulations of water/tert-butanol mixtures.

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