American Chemical Society
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Quantum Chemically Estimated Abraham Solute Parameters Using Multiple Solvent–Water Partition Coefficients and Molecular Polarizability

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posted on 2017-07-25, 00:00 authored by Yuzhen Liang, Ruichang Xiong, Stanley I. Sandler, Dominic M. Di Toro
Polyparameter Linear Free Energy Relationships (pp-LFERs), also called Linear Solvation Energy Relationships (LSERs), are used to predict many environmentally significant properties of chemicals. A method is presented for computing the necessary chemical parameters, the Abraham parameters (AP), used by many pp-LFERs. It employs quantum chemical calculations and uses only the chemical’s molecular structure. The method computes the Abraham E parameter using density functional theory computed molecular polarizability and the Clausius–Mossotti equation relating the index refraction to the molecular polarizability, estimates the Abraham V as the COSMO calculated molecular volume, and computes the remaining AP S, A, and B jointly with a multiple linear regression using sixty-five solvent–water partition coefficients computed using the quantum mechanical COSMO-SAC solvation model. These solute parameters, referred to as Quantum Chemically estimated Abraham Parameters (QCAP), are further adjusted by fitting to experimentally based APs using QCAP parameters as the independent variables so that they are compatible with existing Abraham pp-LFERs. QCAP and adjusted QCAP for 1827 neutral chemicals are included. For 24 solvent–water systems including octanol–water, predicted log solvent–water partition coefficients using adjusted QCAP have the smallest root-mean-square errors (RMSEs, 0.314–0.602) compared to predictions made using APs estimated using the molecular fragment based method ABSOLV (0.45–0.716). For munition and munition-like compounds, adjusted QCAP has much lower RMSE (0.860) than does ABSOLV (4.45) which essentially fails for these compounds.