Apte Pankaj A, Kusaka Isamu
The Koffolt Laboratories, The Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus, Ohio 43210, USA.
J Chem Phys. 2006 May 14;124(18):184106. doi: 10.1063/1.2193148.
We present a new thermodynamic integration method that directly connects the vapor and solid phases by a reversible path. The thermodynamic integration in the isothermal-isobaric ensemble yields the Gibbs free energy difference between the two phases, from which the sublimation temperature can be easily calculated. The method extends to the binary mixture without any modification to the integration path simply by employing the isothermal-isobaric semigrand ensemble. The thermodynamic integration, in this case, yields the chemical potential difference between the solid and vapor phases for one of the components, from which the binary sublimation temperature can be calculated. The coexistence temperatures predicted by our method agree well with those in the literature for single component and binary Lennard-Jones systems.
我们提出了一种新的热力学积分方法，该方法通过一条可逆路径直接连接气相和固相。等温等压系综中的热力学积分给出了两相之间的吉布斯自由能差，由此可以很容易地计算出升华温度。该方法只需采用等温等压半巨正则系综，无需对积分路径进行任何修改即可扩展到二元混合物。在这种情况下，热力学积分给出了其中一个组分在固相和气相之间的化学势差，由此可以计算出二元升华温度。我们的方法预测的共存温度与文献中关于单组分和二元 Lennard-Jones 系统的共存温度吻合良好。
