Shanghai Engineering Research Center of Molecular Therapeutics & New Drug Development, Shanghai Key Laboratory of Green Chemistry & Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
NYU-ECNU Center for Computational Chemistry at NYU Shanghai, Shanghai 200062, China.
J Chem Theory Comput. 2020 Oct 13;16(10):6513-6519. doi: 10.1021/acs.jctc.0c00672. Epub 2020 Sep 30.
A method for accurate calculation of reorganization free energy of an explicit solvent solvating a solute molecule is presented. The method relies on the knowledge of solvation free energy known either from experimental measurement or from accurate calculation. An important part of this approach lies in the calculation of entropy in solute-solvent interaction free energy using the interaction entropy method, combined with the calculation of enthalpy of solvent reorganization based on a finite number of solvent molecules near the solute molecule. This interaction entropy-solvent reorganization or IESR method enables one to compute both enthalpy and entropy components of the solvent reorganization energy from MD simulation of the solvated system. The calculated results are determined by the molecular force field only without any empirical parameter. The current method is applied to computing the reorganization energies of water solvent solvating a wide range of solute molecules including both hydrophilic and hydrophobic ones. The accuracy of the approach is indirectly verified by the excellent agreement of individual enthalpies and entropies of the solvation energies between theory and experiment.
本文提出了一种精确计算显溶剂中溶质分子重组自由能的方法。该方法依赖于溶剂化自由能的知识，这些知识可以通过实验测量或精确计算获得。该方法的一个重要部分在于使用相互作用熵方法计算溶质-溶剂相互作用自由能中的熵，同时根据溶剂分子在溶质分子附近的有限数量计算溶剂重组焓。这种相互作用熵-溶剂重组或 IESR 方法使人们能够从溶剂化体系的 MD 模拟中计算溶剂重组能的焓和熵分量。计算结果仅由分子力场决定，无需任何经验参数。目前的方法被应用于计算包括亲水和疏水在内的各种溶质分子的水溶剂重组能。该方法的准确性通过理论和实验之间的溶剂化能量的个别焓和熵的极好一致性得到间接验证。
