Jaradat Adnan, Al-Salman Rakan, Obeidat Abdalla
Department of Physics, Jordan University of Science and Technology Irbid Jordan
RSC Adv. 2024 Jul 22;14(32):22947-22961. doi: 10.1039/d4ra03494e. eCollection 2024 Jul 19.
Self-diffusion coefficients and shear viscosity coefficients of pure 1-alkanol liquids from methanol to 1-hexanol were predicted using molecular dynamics (MD) simulations. These coefficients have been calculated using the Green-Kubo and Einstein methods at a range of temperatures of 200-330 K with increments of 10 K. Two force fields, TraPPE-UA and OPLS-AA were applied. The predicted results were compared to the experimental data, and the activation energies for self-diffusion and shear viscosity were calculated using the Arrhenius equation. The Stokes-Einstein equation was used to examine its capability in predicting the relationship between self-diffusion and shear viscosity, and the effective hydrodynamic radius was determined using both the experimental data and the results from MD simulations. The TraPPE-UA force field showed better results for the transport properties of methanol, while the OPLS-AA force field performed well for predicting shear viscosity but weakly for self-diffusion, particularly at low temperatures and for 1-alkanol with higher methylene numbers. Using the mean squared displacement method for self-diffusion was found to be more accurate than the Green-Kubo method, while the Green-Kubo method was slightly better for calculating shear viscosity. The Stokes-Einstein equation is valid for pure 1-alkanol liquids with temperature-dependent effective hydrodynamic radius.
采用分子动力学(MD)模拟预测了从甲醇到1-己醇的纯1-链烷醇液体的自扩散系数和剪切粘度系数。这些系数已在200 - 330 K的温度范围内,以10 K的增量,使用格林 - 库博(Green-Kubo)方法和爱因斯坦方法进行了计算。应用了两种力场,即TraPPE-UA和OPLS-AA。将预测结果与实验数据进行了比较,并使用阿仑尼乌斯方程计算了自扩散和剪切粘度的活化能。使用斯托克斯 - 爱因斯坦方程检验其预测自扩散与剪切粘度之间关系的能力,并利用实验数据和MD模拟结果确定了有效流体动力学半径。TraPPE-UA力场对甲醇的传输性质显示出更好的结果,而OPLS-AA力场在预测剪切粘度方面表现良好,但在自扩散方面表现较弱,特别是在低温下以及对于亚甲基数较高的1-链烷醇。发现使用均方位移法计算自扩散比格林 - 库博方法更准确,而格林 - 库博方法在计算剪切粘度方面略胜一筹。斯托克斯 - 爱因斯坦方程对于具有温度依赖性有效流体动力学半径的纯1-链烷醇液体是有效的。