Expanding and Testing a Computational Method for Predicting the Ground State Reduction Potentials of Organic Molecules on the Basis of Empirical Correlation to Experiment

摘要

A method for predicting the ground state reduction potentials of organic molecules on the basis of the correlation ofncomputed energy differences between the starting S0 and one-electron-reduced D0 species with experimental reduction potentialsnin acetonitrile has been expanded to cover 3.5 V of potential range and 74 compounds across 6 broad families of molecules.nUtilizing the conductor-like polarizable continuum model of implicit solvent allows a global correlation that is computationallynefficient and has improved accuracy, with r2 > 0.98 in all cases and root mean square deviation errors of <90 mV (mean absolutendeviations <70 mV) for either B3LYP/6-311+G(d,p) or B3LYP//6-31G(d) with an appropriate choice of radii (UAKS or UA0).nThe correlations are proven to be robust across a wide range of structures and potentials, including four larger (27−28 heavynatoms) and more conformationally flexible photochromic molecules not used in calibrating the correlation. The method is alsonproven to be robust to a number of minor student “mistakes” or methodological inconsistencies.