Determination of excess Gibbs free energy from computer simulation by the single charging‐integral approach. I. Theory
Determination of excess Gibbs free energy from computer simulation by the single charging‐integral approach. I. Theory
复制标题
通过单电荷积分方法通过计算机模拟确定过量吉布斯自由能 I. 理论。
DOI：
10.1063/1.458420
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发表时间：
1990
影响因子：
4.4
通讯作者：
A. Chialvo
中科院分区：
文献类型：
--
作者：
A. Chialvo
最近提出的程序，用于确定过量吉布斯自由能的计算机模拟，由于Chialvo和Haile，并基于柯克伍德的耦合参数解释的化学势，进行了修订和改进。本文导出了新的超额吉布斯自由能、超额焓和超额体积的理论表达式。新方程允许通过等压-等温（NPT）模拟同时确定这些量，该模拟涉及仅来自一个理想溶液的耦合参数充电（即，纯组分），而不管混合物中组分的数目或所涉及的潜在参数的数目。理论表达式推导出允许无限稀释活度系数，纯组分逸度比，和亨利的常数比的测定，而不诉诸无限稀释模拟。
A recently proposed procedure for the determination of excess Gibbs free energy by computer simulation, due to Chialvo and Haile, and based on Kirkwood’s coupling parameter interpretation of the chemical potential, is revised and improved. New theoretical expressions for excess Gibbs free energy, excess enthalpy and excess volume, are derived in this paper. The new equations allow the simultaneous determination of these quantities via isobaric–isothermal (NPT) simulations involving coupling‐parameter charging from only one ideal solution (i.e., pure component), irrespective of either the number of components in the mixture or the number of potential parameters involved. Theoretical expressions are derived which allow the determination of infinite dilution activity coefficients, pure component fugacity ratios, and Henry’s constant ratios without resorting to infinite dilution simulations.