Citation:
LIU Liang-Hong, ZHANG Peng-Fei, HUANG Ying. Molecular Acidity of Singly and Doubly Substituted Phenols: Predictions from Density Functional Reactivity Theory and Hammett Constants[J]. Acta Physico-Chimica Sinica
doi:
10.3866/PKU.WHXB201212071
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Accurate prediction of molecular acidity with ab initio and density functional theory approaches is of great interest, but remains a challenging task. Density functional reactivity theory (DFRT) with quantum descriptors, such as molecular electrostatic potential and valence natural atomic orbital energies, has recently been developed and used for this purpose. Our previous study of substituted benzoic acids revealed a novel approach to quantitatively predict molecular acidity using the Hammett constant, which gave the same prediction accuracy as that of DFRT. In this work, we applied these two approaches to singly and doubly substituted phenol systems, a total of 83 molecules, confirming their effectiveness and robustness. High accuracy was obtained using both approaches, with the DFRT approach achieving slightly higher accuracy than the Hammett approach in general. These results shed further light on the molecular features verning physiochemical properties such as acidity and basicity, both locally on the atomic level and globally on the functional group or molecular level. Our present results confirm the validity of the sum rule of Hammett constants for doubly and multiply substituted compounds.
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