Thermodynamic analysis of the solvent effect on tautomerization of acetylacetone: An ab initio approach

摘要

The keto-enol tautomerism of acetylacetone in solution is studied with the reference interaction site model self-consistent-field (RISM-SCF) method. We choose three solvents, H_2O, dimethyl sulfoxide (DMSO), and carbon tetrachloride (CCl_4), representing, respectively, protic polar, aprotic polar and nanpolar solvents. The analysis is made taking account of the solute electronic as well as geometrical change of the tautomers due to solvent effect. In addition, the electronic correlation energy of solute molecule and solute vibrational energies are considered. The free energy differences are analyzed by decomposing them into the enthalpy and entropy terms. The theory reproduces the total free energy determined by the experiment fairly well. We also find that, as solvent polarities increase, the keto tautomer shows the drastic geometric change in order to make its dipole moment larger and that the geometric change of the keto tautomer is enthalpically driven in H_2O and entropically in DMSO. It is made clear that these depend on the solvent property—protic or aprotic.