Computational study of transition metal coordinated polyaniline: A first principle investigation into tuning the electronic properties of the resulting hybrid material

Abstract

Tuning the electronic properties of polyaniline remains one of the most important features for the development of advanced materials in electronics. In this contribution, we use density functional theory to investigate the electronic properties of polyaniline when coordinating transition metals (Mn, Fe, Co, Cu, Zn) are embedded in the polymer structure.

Importantly, the results reveal that in the presence of transition metal with high electronegativity, the coordinated polyaniline winds up with a decreased gap. Indeed, the band gap for H-PANI decreases from 0.911 eV to 0.513 eV for H-PANI-Mn (lower electronegativity) and to 0.201 eV for H-PANI-Zn (higher electronegativity). This reduction in the energy gap is attributed to enhanced electron delocalization due to increased overlap of electron wavefunctions in the hybrid structure. The results also reveal that the presence of transition metals lead to lower the chemical hardness from 3.252 eV in the case of H-PANI into 0.256 eV for H-PANI-Mn and 0.100 eV for H-PANI-Zn. Additionally, the results from molecular electrostatic potential highlight that PANI-Transition metal sustains more delocalization of charge density distribution compared to H-PANI, leading to molecule polarization which does play a crucial role in various chemical phenomena. These later reveal that the electron density polarization in polyaniline can interestingly be controlled through doping and coordinating the polymer structure with additional transition metals. Therefore, the obtained results might be used in the optimization of electrochemical charge storage in supercapacitors.