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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Sensitivity Analysis of Thermodynamic Properties of Liquid Water:A General Approach to Improve Empirical Potentials
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Sensitivity Analysis of Thermodynamic Properties of Liquid Water:A General Approach to Improve Empirical Potentials

机译：液态水热力学性质的敏感性分析：提高经验电势的通用方法

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摘要

A sensitivity analysis of bulk water thermodynamics is presented in an effort to understand the relation between qualitative features of molecular potentials and properties that they predict.The analysis is incorporated in molecular dynamics simulations and investigates the sensitivity of the Helmholtz free energy,internal energy,entropy,heat capacity,pressure,thermal pressure coefficient,and static dielectric constant to components of the potential rather than the parameters of a given functional form.The sensitivities of the properties are calculated with respect to the van der Waals repulsive and the attractive parts,plus short- and long-range Coulomb parts of three four site empirical water potentials:TIP4P,Dang-Chang and TTM2R.The polarization sensitivity is calculated for the polarizable Dang-Chang and TTM2R potentials.This new type of analysis allows direct comparisons of the sensitivities for different potentials that use different functional forms.The analysis indicates that all investigated properties are most sensitive to the van der Waals repulsive,the short-range Coulomb and the polarization components of the potentials.When polarization is included in the potentials,the magnitude of the sensitivity of the Helmholtz free energy,internal energy,and entropy with respect to this part of the potential is comparable in magnitude to the other electrostatic components.In addition similarities in trends of observed sensitivities for nonpolarizable and polarizable potentials lead to the conclusion that the complexity of the model is not of critical importance for the calculation of these thermodynamic properties for bulk water.The van der Waals attractive and the long-range Coulomb sensitivities are relatively small for the entropy,heat capacity,thermal pressure coefficient and the static dielectric constant,while small changes in any of the potential contributions will significantly affect the pressure.The analysis suggests a procedure for modification of the potentials to improve predictions of thermodynamic properties and we demonstrate this general approach for modifying potentials for one of the potentials.
机译：为了理解分子电势的定性特征与其预测的性质之间的关系，本文对散装水的热力学进行了敏感性分析。该分析被纳入分子动力学模拟，并研究了亥姆霍兹自由能，内能，熵的敏感性，热容量，压力，热压力系数和静态介电常数对电位分量的影响，而不是给定功能形式的参数。相对于范德华排斥力和有吸引力的部分，计算出性质的敏感性TIP4P，Dang-Chang和TTM2R这三个四个位置的水位电势的短程和远程库仑部分，计算极化极化Dang-Chang和TTM2R电势的极化灵敏度，这种新型分析方法可以直接比较灵敏度针对使用不同功能形式的不同潜力。分析表明，所研究的性质对范德华排斥力，短程库仑和电势的极化分量最敏感。当电势中包括极化时，亥姆霍兹自由能，内部能和熵的灵敏度大小相对于这部分电势，其大小可与其他静电分量相媲美。此外，对于不可极化和可极化电势，观察到的敏感度趋势的相似之处还导致结论，即模型的复杂性对于计算对于熵，热容量，热压系数和静态介电常数，范德华吸引力和远距离库仑灵敏度相对较小，而任何潜在贡献的微小变化都将显着影响范德华力和远距离库仑灵敏度。分析提出了修改p的程序潜力，以改善对热力学性质的预测，我们演示了这种通用方法，可针对其中一种潜力修改潜力。

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