A DFT study of 3d (d1-d10) transition-metal phthalocyanines (TMPcs): Bonding natures, electronic adsorption spectroscopy

The structures, electronic properties, bonding characters and UV-Vis spectra of 3d (d(1)-d(10)) transition-metal phthalocyanines (TMPcs) molecules have been studied with different density function theory (DFT) methods. The calculated structural parameters agree well with previous experimental or theoretical values. Natural Population Analysis (NPA) charge revealed that 4s-3d/4p hybridizations occur when 3d TM atoms are involved in chemical bondings. The spin magnetic moments of TMPcs are mainly from the contribution of 3d electrons. Conceptual density functional theory (CDFT) results indicate that 3d TMPcs molecules are willing to accept further electrons. The TM-N chemical bonds show very weak covalent nature, and are consistent with bond order analyses. Time-dependent density function theory (TD-DFT) calculations were carried out to simulate the UV-Vis spectra, and corresponding electronic transfers for dominant peaks were also obtained.