Expanding and testing a computational method for predicting the ground state reduction potentials of organic molecules on the basis of empirical correlation to experiment

J Org Chem. 2012 Aug 3;77(15):6423-30. doi: 10.1021/jo300853k. Epub 2012 Jul 16.

Abstract

A method for predicting the ground state reduction potentials of organic molecules on the basis of the correlation of computed energy differences between the starting S(0) and one-electron-reduced D(0) species with experimental reduction potentials in acetonitrile has been expanded to cover 3.5 V of potential range and 74 compounds across 6 broad families of molecules. Utilizing the conductor-like polarizable continuum model of implicit solvent allows a global correlation that is computationally efficient and has improved accuracy, with r(2) > 0.98 in all cases and root mean square deviation errors of <90 mV (mean absolute deviations <70 mV) for either B3LYP/6-311+G(d,p) or B3LYP//6-31G(d) with an appropriate choice of radii (UAKS or UA0). The correlations are proven to be robust across a wide range of structures and potentials, including four larger (27-28 heavy atoms) and more conformationally flexible photochromic molecules not used in calibrating the correlation. The method is also proven to be robust to a number of minor student "mistakes" or methodological inconsistencies.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Molecular Structure
  • Organic Chemicals / chemistry*
  • Oxidation-Reduction
  • Quantum Theory*

Substances

  • Organic Chemicals