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Statistical mechanics of monatomic liquids

机译:单原子液体的统计力学

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Two key experimental properties of elemental liquids, together with an analysis of the condensed-system potential-energy surface, lead us logically to the dynamical theory of monatomic liquids. Experimentally, the ion motional specific heat is approximately 3Nk for N ions, implying the normal modes of motion are approximately 3N independent harmonic oscillators. This implies the potential surface contains nearly harmonic valleys. The equilibrium configuration at the bottom of each valley is a ''structure.'' Structures are crystalline or amorphous, and amorphous structures can have a remnant of local crystal symmetry, or can be random. The random structures are by far the most numerous, and hence dominate the statistical mechanics of the liquid state, and their macroscopic properties are uniform over the structure class, for large-hi systems. The Hamiltonian for any structural valley is the static structure potential, a sum of harmonic normal modes, and an anharmonic correction. Again from experiment, the constant-density entropy of melting contains a universal disordering contribution of Nk Delta, suggesting the random structural valleys are of universal number w(N), where lnw=Delta. Our experimental estimate for Delta is 0.80. In quasiharmonic approximation, the liquid theory for entropy agrees with experiment, for all currently analyzable experimental data at elevated temperatures, to within 1-2% of the total entropy. Further testable predictions of the theory are mentioned.
机译:元素液体的两个关键实验性质,以及对冷凝系统势能面的分析,从逻辑上将我们引向了单原子液体的动力学理论。实验上,N个离子的离子运动比热约为3Nk,这意味着正常的运动模式约为3N个独立的谐波振荡器。这意味着潜在表面包含近乎谐波的谷。每个凹谷底部的平衡构型为“结构”。结构为晶体或非晶态,非晶态结构可能具有局部晶体对称性,也可以是随机的。迄今为止,无规结构数量最多,因此在液态统计力学中占主导地位,并且对于大型hi系统,其宏观性质在结构类别上是一致的。任何结构谷的哈密顿量都是静态结构势,谐波正态模和和非谐校正。再次从实验中,熔化的恒定密度熵包含Nk Delta的普遍无序贡献,表明随机结构的波谷具有普遍数w(N),其中lnw = Delta。我们对Delta的实验估算为0.80。在准谐波近似中,熵的液体理论与实验相吻合,对于所有当前可分析的高温实验数据,其熵均在总熵的1-2%之内。提到了该理论的其他可验证的预测。

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