F. Bouchelaghem, H. Boutarfa, M. Chicouche, S. Lias
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引用次数: 0
摘要
背景:由于统计物理学和量子力学第一次成功地结合在一起,部分归功于查普曼、考林和赫斯菲尔德的工作。广泛的理论和实验研究一直致力于理解气体和气体混合物的动力学。在其他成就中,这种整合在理论上建立了气体的宏观特性(无论是测量的还是计算的)与其组成粒子的量子特性之间的直接联系。该模型成功地建立了直接的数学关系,将气体的原子和/或分子组分之间的微观相互作用与可测量的输运性质(如扩散和粘度系数)联系起来。它还解释了这些性质是如何变化的,以及它们是如何受到热力学参数(如压力、密度和温度)的影响的。方法:利用从头计算和实验测量两种方法获得电位数据。势V(R)的从头计算值是从分子问题的量子理论方法中得到的。通常,这些方法提供在特定范围内核间距离R的离散值处的势能。为了建立与基本相互作用相对应的势能曲线,我们将依靠从头算数据。知道了这个势,就可以使用Numerov方法对径向波动方程进行数值求解,最终可以计算相移η E。根据弹性碰撞相移,我们利用Chapman-Enskog模型推导出了自扩散系数D、粘度η和导热系数λ。对于扩散和粘度,我们在计算时考虑了对称效应和自旋效应,这些效应与碰撞粒子的相同性质有关。然后,我们研究了这些输运系数如何随温度变化,并提出了一种简单的计算方法来获得D(T), η (T)和λ (T)的解析表达式。
New determination of the thermophysical properties of argon gas considering nuclear spin and symmetry effects
Context
Since statistical physics and quantum mechanics were first successfully combined thanks in part to the work of Chapman and Cowling and Hirschfelder. Extensive theoretical and experimental research has been dedicated to understanding the kinetics of gases and gas mixtures. This integration has, among other achievements, theoretically established a direct link between the macroscopic properties of gases whether measured or calculated and the quantum characteristics of their constituent particles. This model successfully established straightforward mathematical relationships linking the microscopic interactions between the atomic and/or molecular components of a gas to measurable transport properties, such as diffusion and viscosity coefficients. It also provided explanations for how these properties vary and how they are influenced by thermodynamic parameters like pressure, density, and temperature.
Methods
The potential data available to us are either obtained from ab initio calculations or experimental measurements. The ab initio values of the potential V(R) are derived from a quantum-theoretical approach to the molecular problem. Typically, these methods provide the potential energy at discrete values of the internuclear distance R within a specified range. To build the potential energy curve corresponding to the fundamental interactions, we will rely on ab initio data. Knowing this potential allows for the numerical solution of the radial wave equation using Numerov’s method, ultimately enabling the calculation of the phase shifts \(\eta \left( E\right) \). From the elastic collision phase shifts, we derive the self-diffusion coefficient D, viscosity \(\eta \), and thermal conductivity \(\lambda \) using the Chapman-Enskog model. For diffusion and viscosity, we perform calculations both with accounting for the symmetry and spin effects associated with the identical nature of the colliding particles. We then examine how these transport coefficients vary with temperature and propose a straightforward computational approach to obtain analytical expressions for D(T), \(\eta (T)\), and \(\lambda (T).\)
期刊介绍:
The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling.
Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry.
Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.