用分子密度泛函理论精确计算超临界CO₂中的溶剂化性质
Accurate Solvation Properties in supercritical CO$_2$ with Molecular Density Functional Theory
AI总结：
研究超临界CO₂溶剂化性质，用基于特定密度的分子cDFT形式，以低计算成本准确重现其溶剂化性质，还研究了cDFT中过剩自由能泛函近似水平，为扩展分子cDFT到其他热力学条件开辟道路。
AI中文摘要：
超临界CO₂是用于开发更环保化学过程的高效溶剂。准确且低成本预测其溶剂化性质（溶剂化自由能和溶剂化结构）至关重要。本文表明经典密度泛函理论（cDFT）能重现传统分子模拟得到的溶剂化性质，且计算量低几个数量级。通过基于依赖溶质附近CO₂分子位置和取向的密度的分子cDFT形式实现了良好一致性。还研究了cDFT中过剩自由能泛函的几种近似水平，证明均匀参考流体近似足以恢复分子动力学（MD）基准结果。这些发现为将分子cDFT扩展到其他热力学条件开辟了道路。
英文摘要：
Supercritical CO$_2$ is a highly efficient solvent for the development of more environmentally benign chemical processes. It is crucial to predict its solvation properties -- the solvation free energy and the solvation structure -- both accurately and at low computational cost. We show here that classical density functional theory (cDFT) can reproduce the solvation properties obtained from conventional molecular simulations, while requiring a computational effort that is several orders of magnitude lower. This excellent agreement is achieved using a molecular cDFT formalism based on a density that depends on both the positions and orientations of CO$_2$ molecules in the vicinity of the solute. We further examine several levels of approximation for the excess free-energy functional in cDFT and demonstrate that the homogeneous reference fluid approximation is sufficient to recover the molecular dynamics (MD) benchmark results. These findings open the way to extending molecular cDFT to other thermodynamic conditions.
