Statistical thermodynamics in the classical molecular dynamics ensemble. I. Fundamentals
Statistical thermodynamics in the classical molecular dynamics ensemble. I. Fundamentals
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经典分子动力学系综中的统计热力学。
DOI：
10.1063/1.466446
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发表时间：
1994
影响因子：
4.4
通讯作者：
R. Lustig
中科院分区：
文献类型：
--
作者：
R. Lustig
在分子动力学系综中考虑了由刚性分子组成的经典系统的统计热力学。将玻尔兹曼S=kB ln W作为统计力学的基本假设，导出了W的两种经典选择的精确形式。由于热力学导数的顺序没有限制，所以在这个系综中任何可测量的量都是直接可得的。给出了亥姆霍兹能导数的显式统计类比，包括化学势的近似值。确定了基本相空间函数并探讨了它们的性质。证明了完整的热力学是由这些函数从普遍行为引起的微小扰动所控制的。
The statistical thermodynamics of a classical system composed of rigid molecules is considered in the molecular dynamics ensemble. Accepting Boltzmann’s S=kB ln W as the basic assumption of statistical mechanics, exact formalisms for two classical choices of W are derived. Since there are no restrictions on the order of thermodynamic derivatives, any measurable quantity is directly accessible in this ensemble. Explicit statistical analogs are given for the derivatives of the Helmholtz energy including an approximation for the chemical potential. Basic phase space functions are identified and their properties are explored. It is shown that the complete thermodynamics is governed by small perturbations of these functions from universal behavior.