Assessing the thermodynamic signatures of hydrophobic hydration for several common water models
Assessing the thermodynamic signatures of hydrophobic hydration for several common water models
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DOI：
10.1063/1.3366718
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发表时间：
2010-03-28
影响因子：
4.4
通讯作者：
Staton, Jennifer A.
中科院分区：
文献类型：
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作者：
Ashbaugh, Henry S.;Collett, Nicholas J.;Staton, Jennifer A.
根据信息论分析的结论，即疏水水化是由液态水的状态方程决定的，我们对10个不同的水模型进行了模拟，以检验每个模型对液态水的实验密度的保真度与其对甲烷水化的描述的准确性之间的相关性。我们发现，与四点水模型相比，三点水模型和五点水模型对液体密度和甲烷溶解度的描述都较差。在四点水模型中，TIP4P/2005对水相状态方程和甲烷水化热力学都提供了最好的描述。将优化后的势用于甲烷的液态模拟联合原子描述时，发现甲烷水合反应的熵和热容与实验符合得很好，但化学势和热能有系统的上移。随后，我们重新优化了甲烷相互作用，通过考虑丢失的吸引相互作用，准确地再现了实验中的溶解度作为温度的函数。
Following the conclusions of an information theory analysis that hydrophobic hydration is dictated by the equation of state of liquid water, we perform simulations of ten different water models to examine the correlation between the fidelity of each model to the experimental density of liquid water and the accuracy of its description of methane hydration. We find that the three- and five-point water models provide an inferior description of both the liquid density and methane solubility compared to the four-point water models. Of the four-point water models, TIP4P/2005 provides the best description of both the aqueous equation-of-state and methane hydration thermodynamics. When the optimized potentials for liquid simulation united-atom description for methane is used, we find that while the entropy and heat capacity of methane hydration are in excellent agreement with experiment, the chemical potential and enthalpy are systematically shifted upwards. We subsequently reoptimize the methane interaction to accurately reproduce the experimental solubilities as a function of temperature by accounting for missing attractive interactions.