Chong Song-Ho, Ham Sihyun
Department of Chemistry, Sookmyung Women's University , Cheongpa-ro 47-gil 100, Yongsan-Ku, Seoul 140-742, Korea.
J Chem Theory Comput. 2015 Feb 10;11(2):378-80. doi: 10.1021/ct500876x. Epub 2015 Jan 12.
Solvation free energy is the fundamental thermodynamic quantity in solution chemistry. Recently, it has been suggested that the partial molar volume correction is necessary to convert the solvation free energy determined in different thermodynamic ensembles. Here, we demonstrate ensemble-independence of the solvation free energy on general thermodynamic grounds. Theoretical estimates of the solvation free energy based on the canonical or grand-canonical ensemble are pertinent to experiments carried out under constant pressure without any conversion.
溶剂化自由能是溶液化学中的基本热力学量。最近，有人提出，为了转换在不同热力学系综中测定的溶剂化自由能，部分摩尔体积校正必不可少。在此，我们基于一般热力学原理证明了溶剂化自由能的系综独立性。基于正则系综或巨正则系综对溶剂化自由能进行的理论估算，适用于在恒压条件下进行的实验，无需任何转换。
