Theoretical study of electronic absorptions in aminopyridines – TCNE CT complexes by quantum chemical methods, including solvent

Abstract

The geometric and electronic structure of donor-acceptor complexes of TCNE with aniline, o-, m- and p- aminopyridines and pyridine has been studied in gas phase and in solution using CC2, TDDFT and CIS methods. Concerning interaction energy between particular donor and TCNE acceptor it is fairly described by both CC2 (MP2) and DFT-D approaches. Transition energies in gas phase calculated by CC2 approach are in good agreement with available experimental data for aniline. TDDFT calculations with LC-BLYP functional (with standard value of range separation factor μ = 0.47) gives transition energies too high although not as high as CIS. The red solvent shifts, calculated by PCM model with CIS method are qualitative correct, but error in the range of 0.1-0.2 eV should be expected.