Localization and relaxation of singlet exciton formation in conjugated polymers under photoexcitation.

This paper employs a molecular dynamics approach to uncover the time profile of exciton formation, which can be divided into two stages: localization of electron-hole pairs and relaxation process (nuclear and electronic). Under photoexcitation, an electron-hole pair is formed by an electronic transition, and the pair in turn becomes localized through the electron-lattice interaction, which triggers the total energy to shift violently and oscillate. The oscillation during the first 40 fs induces the excitation to step into the second stage, i.e., relaxation. After the relaxation process of about 850 fs, the total energy, lattice energy, and electron energy reach certain values whereas the lattice configuration and electron remain localized, indicating the formation of a singlet exciton.