DFT-based linear solvation energy relationships for the infrared spectral shifts of acetone in polar and nonpolar organic solvents.
Linear solvation energy relationships (LSER) established using solvation free energy and density functional theory (DFT)-based reactivity descriptors are for the first time documented in this study. The solvent-induced shifts of the carbonyl (C=O) stretching frequency of acetone in 21 organic solvents including polar protic, dipolar aprotic, and nonpolar solvents are examined. Results of the multiple regression analysis have shown that four descriptors, namely, (1) the solvation free energy of solute in continuous dielectric medium, (2) the global interaction energy of the solute-solvent system, (3) the maximum electrostatic potential on the hydrogen atom of the solvent molecule, and (4) the maximum condensed nucleophilic Fukui function (or nucleophilic condensed local softness) of the solvent molecule, those which considered both the nonspecific and specific effects of solute-solvent interactions, can be incorporated in a multiparameter equation for constructing the present DFT-based LSER.
Chang
Chia M
CM
Environmental Molecular and Electromagnetic Physics Laboratory, Department of Soil and Environmental Sciences, National Chung Hsing University, Taichung 402, Taiwan. abinitio@dragon.nchu.edu.tw
D000096:Acetone / Q000737:chemistry*; D016014:Linear Models; D008956:Models, Chemical; D011789:Quantum Theory; D012996:Solutions; D012997:Solvents / Q000737:chemistry*; D055672:Static Electricity; D013816:Thermodynamics
D012996:Solutions; D012997:Solvents; D000096:Acetone