Hybrid Functional Analysis of Electronic Properties of Transition-Metal Phthalocyanines

Abstract

This work presents the ab initio study of transition-metal phthalocyanines within a PBE0 hybrid functional. The list of metal impurities includes manganese, iron, cobalt, nickel, copper, and zinc. All calculations of isolated molecules have been performed with the use of the projector augment-wave method. For iron phthalocyanine, we have performed four calculations with different values of the mixing parameter a (the value of the exact exchange) – 0, 1/4, 1/3, and 1/2. For all other molecules, the calculations have been performed for a = 1/4 and 1/3. The electronic structure parameters including the HOMO-LUMO energy gap, Fermi level, magnetization, and imaginary part of the dielectric function are presented and compared with available theoretical and experimental data. Manganese, iron, and cobalt phthalocyanines show a strong dependence of electronic properties on the value of the exact exchange interaction. In other molecules with nickel, copper, and zinc, this dependence is not significant.