Expanding and testing a computational method for predicting the ground state reduction potentials of organic molecules on the basis of empirical correlation to experiment.
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.
Department of Chemistry, Hope College, 35 E. 12th Street, Holland, Michigan 49423, USA.
Eugene J
EJ
Lynch
Amy L
AL
Speelman
Bryce A
BA
Curry
Charles S
CS
Murillo
Jason G
JG
Gillmore
D015394:Molecular Structure; D009930:Organic Chemicals / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory
D009930:Organic Chemicals