Theoretical studies on metal porphyrin halides: geometrical parameters and nonlinear optical responses

The geometrical parameters and static electric properties of several metal porphyrin halides, including Fe(III) porphine chloride (FePCl), Fe(III) porphine bromide (FePBr), Fe(III) tetraphenylporphine chloride (FeTPPCl), aluminum phthalocyanine chloride (AlPcCl), gallium(III) phthalocyanine chloride (GaPcCl), and manganese(III) phthalocyanine chloride (MnPcCl), were investigated using density functional theory (DFT) methods. It was observed that FePBr and MnPcCl showed the highest total hyperpolarisabilities among the studied porphyrins. To investigate the effect of substituted phenyl groups on the nonlinear optical (NLO) responses of porphyrins, the optical properties of FeTPPCl and FePCl were compared using UBLYP/cc-pVDZ+LanL2DZ level of theory. Moreover, the polarised continuum model (PCM) was employed to study the influence of solvation on the optical properties of FePCl.