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Modeling velocity autocorrelation functions for confined fluids using gamma distributions

机译:使用 gamma分布对承压流体的速度自相关函数建模

摘要

We propose a model for the short-time dynamics of fluids confined in slit-shaped pores. The model has been developed from the observation that the real lobe of the instantaneous normal mode density of states (INM DOS) closely follows a gamma distribution. By proposing that the density of states of the confined fluid can be represented by a gamma distribution, the resulting velocity autocorrelation function (VACF) is constructed such that it is accurate upto the fourth frequency moment. The proposed model results in an analytical expression for the VACF and relaxation times. The VACFs obtained from the model have been compared with the VACFs obtained from molecular dynamic simulations and INM analysis for fluids confined in slit-shaped pores over a wide range of confinement and temperatures. The model is seen to capture the short-time behavior of the VACF extremely accurately and in this region is superior to the predictions of the VACF obtained from the real lobe of the INM DOS. Although the model predicts a zero self-diffusivity, the predicted relaxation times are in better agreement with the molecular dynamics results when compared with those obtained from the INM theory.
机译:我们提出了一种狭缝形孔内流体短期动态模型。该模型是根据以下观察结果开发的:瞬时法向态态密度(INM DOS)的真实波瓣紧密遵循γ分布。通过提出承压流体的状态密度可以用γ分布表示,构造了最终的速度自相关函数(VACF),使其在第四频率矩之前都是精确的。所提出的模型得出了VACF和松弛时间的解析表达式。已将从模型获得的VACF与从分子动力学模拟和INM分析获得的VACF进行了比较,这些流体是在宽范围的限制和温度范围内限制在狭缝状孔中的流体。该模型可以非常精确地捕获VACF的短时行为,并且在该区域内优于从INM DOS的真实波瓣获得的VACF的预测。尽管该模型预测的自扩散率为零,但与从INM理论获得的结果相比,预测的弛豫时间与分子动力学结果更好地吻合。

著录项

  • 作者

    Krishnan SH; Ayappa KG;

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  • 年度 2004
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