Forbidden Singlet Exciton Transitions Induced by Localization in Polymer Light-Emitting Diodes in a Strong Electric Field

Through combining the electron transition process and dipole moment evolution as well as electron-phonon coupling, molecular dynamics calculations show that the radiative decay of, singlet excitons in a conjugated polymer, such as a polymer light-emitting diode (PLED), is largely determined by the evolution of the dipole moment. Without an electric field, the decay life of a singlet, exciton is about 1 ns. Once an electric field is applied and exceeds a critical value, with electron-phonon coupling, the original lattice structure evolves into two new localized lattice distortions, consistent with the experimental results. Owing to the new lattice structure and self-trapping, the dipole moment rapidly decreases to zero within 5 fs, eliminating the radiative decay of the singlet exciton.