单原子液体渡越自由能的统计力学模型
Statistical mechanics model for the transit free energy of monatomic liquids
摘要：
在将液体动力学的振动-渡越（V-T）理论应用于单原子液体的热力学性质时，已经达到了需要改进的模型来处理小（约100%）的点。10%）的过境贡献。为了实现这一目标，最近完成了对元素液体的高温实验熵数据的分析[D。C. Wallace，E. D. Chisolm和N. Bock，Phys.Rev.B79，051201（2009）]。这种分析得到了一条通用的渡越熵与T/θ tr的关系曲线，其中T是温度，θ tr是每个元素的标度温度。本文建立了过渡配分函数的统计力学模型，并根据实验得到的过渡熵曲线进行了标定。该模型有两个标量参数，并捕捉到实验的温度标度。校准后的模型拟合实验液体熵在所有温度下的高精度。在没有附加参数的情况下，该模型对于Na的内能与T的关系也与实验和分子动力学一致。V-T理论通过校准的渡越模型提供了单原子液体热力学性质的从头计算方程。这将允许该理论的适用范围，以及其整体的准确性，以确定。更一般地说，V-T理论的假设，将多原子势能谷分为随机和对称的类别，也可以测试其在单原子系统之外的应用。
英文摘要：
In applying Vibration-Transit (V-T) theory of liquid dynamics to the thermodynamic properties of monatomic liquids, the point has been reached where an improved model is needed for the small (approx. 10%) transit contribution. Toward this goal, an analysis of the available high-temperature experimental entropy data for elemental liquids was recently completed [D. C. Wallace, E. D. Chisolm, and N. Bock, Phys. Rev. B 79, 051201 (2009)]. This analysis yields a common curve of transit entropy vs. T/θ_{tr}, where T is temperature and θ_{tr} is a scaling temperature for each element. In the present paper, a statistical mechanics model is constructed for the transit partition function, and is calibrated to the experimental transit entropy curve. The model has two scalar parameters, and captures the temperature scaling of experiment. The calibrated model fits the experimental liquid entropy to high accuracy at all temperatures. With no additional parameters, the model also agrees with both experiment and molecular dynamics for the internal energy vs. T for Na. With the calibrated transit model, V-T theory provides equations subject to ab initio evaluation for thermodynamic properties of monatomic liquids. This will allow the range of applicability of the theory, and its overall accuracy, to be determined. More generally, the hypothesis of V-T theory, which divides the many-atom potential energy valleys into random and symmetric classes, can also be tested for its application beyond monatomic systems.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
