Computational electrochemistry of the two-step reduction potentials of some quinones using DFT response combined with CPCM continuum solvation model in acetonitrile

Abstract

DFT calculations have been performed using B3LYP with 6-31G* and 6-31G** basis sets in combination with CPCM (COSMO) dielectric continuum model to investigate two stepwise reduction potentials for eight different quinone derivatives in acetonitrile solution. The electrode potentials of quinone molecules were calculated relative to a reference molecule and compared with the experimental findings. The root mean square errors (r.m.s.) of the calculations based on B3LYP/6-31G* and B3LYP/6-31G** methods found to be 0.14 and 0.12 V, respectively. Analysis of correlation between the experimental electrode reduction potentials and the theoretically calculated values revealed that notable relations existed between the two stepwise reduction electrode potentials and the eigenvalues of LUMOs of the quinone derivatives. Show more