Density Functional Theory Study of Poly(<i>o</i>‑phenylenediamine) Oligomers

Abstract

Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been performed to gain insight into the structure of poly­(<i>o</i>-phenylenediamine) (POPD). Both reported structures of POPD, ladder (L)- and polyaniline (P)-like, are investigated theoretically through the oligomers approach. The simulated vibrational properties of 5POPD­(L) and 5POPD­(P) at B3LYP/6-31G (d) along with their assignments are correlated with experimental frequencies. Vibrational spectra show characteristic peaks for both POPD­(L) and POPD­(P) structures and do not provide any conclusive evidence. Excited-state properties such as band gap, ionization potential, electron affinities, and HOMO–LUMO gaps of POPD­(L) and POPD­(P) from monomers to five repeating units are simulated. UV–vis spectra are simulated at the TD-B3LYP/6-31+G (d, p) level of theory, supportive to the ladder-like structure as the major contributor. Comparison of the calculated data with the experimental one strongly suggests that the ladder-like structure is the predominant contributor to the molecular structure of POPD; however, a small amount of POPD­(P) is also believed to be present