论文标题

缝隙孔中单相流体的纳米热动力学描述和分子模拟

Nanothermodynamic description and molecular simulation of a single-phase fluid in a slit pore

论文作者

Galteland, Olav, Bedeaux, Dick, Kjelstrup, Signe

论文摘要

我们使用丘陵的小型系统的热力学描述了高度限制的单相和单一组分流体的热力学状态。该理论最近被命名为纳米热力学。我们首先构建一个缝隙孔的合奏,以用于受控温度,体积,表面积和化学势。我们根据Hill介绍积分和差异性能,并使用它们来定义不加压力。我们以一致的方式通过其机械对应物来识别所有热力学压力,并通过分子动力学模拟研究识别。我们定义和计算不结合压力,并表明其包含标准定义。我们计算熵和能量密度,并发现与文献一致,即墙壁上的力具有能量,而不是熵的性质。对于具有大壁的缝隙孔的细分电势为零,但对于相关的控制变量集,不相等。我们展示了如何使用Hill的方法来找到狭窄的流体的新麦克斯韦关系,除了缩放关系外,当墙壁分离得足够远时,该方法适用于缩放关系。通过纳米热力学的这种扩展,我们为进一步发展的纳米技术中核心的热力学的进一步发展奠定了基础。

We describe the thermodynamic state of a highly confined single-phase and single-component fluid in a slit pore using Hill's thermodynamics of small systems. This theory was more recently named nanothermodynamics. We start by constructing an ensemble of slit pores for controlled temperature, volume, surface area, and chemical potential. We present the integral and differential properties according to Hill, and use them to define the disjoining pressure. We identify all thermodynamic pressures by their mechanical counterparts in a consistent manner, and investigate the identification by molecular dynamics simulations. We define and compute the disjoining pressure, and show that it contains the standard definition. We compute the entropy and energy densities, and find in agreement with the literature, that the forces at the wall are of an energetic, not entropic nature. The subdivision potential is zero for this slit pore with large walls, but unequal to zero for related sets of control variables. We show how Hill's method can be used to find new Maxwell relations of a confined fluid, in addition to a scaling relation, which applies when the walls are separated far enough. By this expansion of nanothermodynamics, we set the stage for further developments of the thermodynamics of confined fluids, a field that is central in nanotechnology.

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