Time-dependent density functional theory study on the excited-state hydrogen-bonding characteristics of polyaniline in aqueous environment

• The excited-state hydrogen-bonding characteristics of PANI were studied.
• The hydrogen bonds CN ⋯ HO and NH ⋯ OH can be formed in the complexes.
• The hydrogen-bonding strengthening was demonstrated upon photoexcitation.
• H-bond strengthening plays an important role in the internal conversion process.

A theoretical study was carried out to study the excited-state of hydrogen-bonding characteristics of polyaniline (PANI) in aqueous environment. The hydrogen-bonded PANI-H2O complexes were studied using first-principles calculations based on density functional theory (DFT). The electronic excitation energies and the corresponding oscillator strengths of the low-lying electronically excited states for hydrogen-bonded complexes were calculated by time-dependent density functional theory (TDDFT). The ground-state geometric structures were optimized, and it is observed that the intermolecular hydrogen bonds CN ⋯ HO and NH ⋯ OH were formed in PANI-H2O complexes. The formed hydrogen bonds influenced the bond lengths, the charge distribution, as well as the spectral characters of the groups involved. It was concluded that all the hydrogen-bonded PANI-H2O complexes were primarily excited to the S1 states with the largest oscillator strength. In addition, the orbital transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) involved intramolecular charge redistribution resulting to increase the electron density of the quinonoid rings.

Figure optionsDownload as PowerPoint slide