The accuracy of force fields is a key to the successful prediction of the thermodynamic properties of materials. In simulations of organic molecules over large temperature ranges, atomistic force fields that are parametrized at, or near, ambient temperatures are found to systematically underestimate the intermolecular dispersion interactions at elevated temperatures. Analysis of the underestimates using diatomic molecules indicates that a minor part is due to the change in molecular polarizability, while the major part is due to the reduced dielectric constant of the bulk liquid as the density decreases with increasing temperature. By establishing the dispersion parameter as a linear function of temperature, we have successfully enhanced the temperature transferability of atomistic force fields. This approach is tested on 66 molecular liquids covering four functional groups – alkane, aromatic, ether, and ketone-aldehyde – over a broad range of temperatures by calculating liquid density, heat of vaporization, isobaric heat capacity, and shear viscosity.

中文翻译：

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色散相互作用力场参数的温度传递性

力场的准确性是成功预测材料热力学性质的关键。在较大温度范围内对有机分子进行模拟时，发现在环境温度或环境温度附近参数化的原子力场会系统地低估了高温下的分子间色散相互作用。使用双原子分子对低估进行的分析表明，一小部分是由于分子极化率的变化引起的，而一大部分是由于随着温度的升高密度降低，本体液体的介电常数降低了。通过将色散参数建立为温度的线性函数，我们成功地增强了原子力场的温度传递性。