CORRELATION OF VOLTAMMETRIC AND SPECTROSCOPIC DATA OBTAINED FROM OPEN-SHELL AND CLOSED-SHELL AROMATIC ESTERS AND THOSE OBTAINED FROM AM1 CALCULATIONS

Results from semi-empirical molecular orbital calculations on a series of pyridine and benzene esters and thioic S-esters (closed-shell) and their associated anion radicals (open-shell) using the MOPAC computer program, the AMI Hamiltonian and the RHF and UHF methods, have been c ompared with electrochemical and spectroscopic experimental data obtai ned in acetonitrile solution containing 0.1 M supporting electrolyte ( Et4NPF6). The experimental data considered an reversible half-wave pot entials obtained by differential pulse voltammetry and/or cyclic volta mmetry, hyperfine splitting constants obtained by in situ electrochemi cal EPR experiments and absorption spectra obtained by in situ electro chemistry-UV-Vis spectroscopy. (C) 1998 Elsevier Science S.A.