| As building blocks of anisotropic electrically conductive molecular crystal and polymeric substances, metalloporphyrins have been of particular value in exploration of the relationship between the atomic-level architecture and macroscopic transport properties. Theoretical investigation is necessary to be incorporated with experimental information to understand the physical and chemical behavior of the systems and to guide new material design. Using the local density approximation and the discrete variational method, we systematically studied the electronic structure, optical and magnetic response properties of these metalloporphyrins: CuTap, CuPc, CoPc, NiPc and NiTbp.; Self-consistent calculations of partially oxidized CuTap give a quantitative measure of the electron donor characteristics shared by the intimate mixture of Cu-d and N, C-{dollar}pi{dollar} orbitals. The comparison of CuTap and CuPc indicates that benzene components are dominated in the lower energy valence band. The metal substitution of Cu by Ni leads to a delocalization of d-character over the entire valence band; and Co substitution leads to a stronger d-character around the Fermi energy.; The in-plane polarized theoretical optical spectra successfully reproduce the overall experimental absorption pattern. The irregularity of optical spectra associated with thesis M-Pcs in the literature are attributed to the modulation of the different metal-ring couplings. Calculated out-of-plane transitions are too weak compared to the molecular crystal experiment, which suggests the importance of intermolecular coupling.; To fulfill the needs of obtaining theoretical value of magnetic susceptibility and chemical shift for molecules that orbital magnetic responses are not negligible, we developed a method based on DVM. This new method is feasible for large molecules while overcoming the major difficulty of requiring huge basis sets that traditional perturbation theory encountered. |
