The DFT Quantum Chemistry Study of the Simplest Alkylthio Radicals

摘要

The electron affinities of the simplest alkylthio radicals have been examined using four hybrid Hartree-Fock/density functional methods. The basis set used in this work is of double-ζ plus polarization quality with additional diffuse s-and p-type functions. Three different types of the neutral-anion energy separations reported in this work are the adiabatic electron affinity (EAad), the vertical electron affinity (EA_(vert)), and the vertical detachment energy (VDE). The most reliable adiabatic electron affinities, obtained at the DZP++ B3LYP level of theory, are 1.93 eV (C_2H_5S), 1.93 eV (a-C_3H_7S), 2.02 eV (b-C_3H_7S), 1.94 eV (a-C_4H_9S), 1.95 eV (b-C_4H_9S), 2.07 eV (a-C_5H_(11)S), 2.08 eV (b-C_5H_(11)S), 2.09 eV (c-C_5H_(11)S), respectively. Compared with the experimental values, the average absolute error of the B3LYP method is 0.04 eV.