Journal of Chemical Physics, Vol.112, No.17, 7684-7692, 2000
A quantum molecular dynamics study of exciton self-trapping in conjugated polymers: Temperature dependence and spectroscopy
We examine the dynamics of exciton self-trapping in conjugated polymer systems using mixed quantum-classical molecular dynamics. The model treats the exciton as a two-dimensional quantum mechanical wave function representing a particle/hole quasiparticle interacting with a classical vibrational lattice [M. N. Kobrak and E. R. Bittner, J. Chem. Phys. 112, 5399 (2000)]. We show that the dynamics are influenced strongly by thermal disorder in the lattice, and that there is a dramatic change in the self-trapping mechanism as temperature increases. At low temperatures, the rate of localization is limited by the time required for the vibrational lattice to respond to the creation of the particle-hole pair, while at higher temperatures thermal disorder permits localization on time scales limited primarily by electronic response. We simulate the time-resolved fluorescence spectrum for the model system, and compare the temperature dependence of the spectrum to recent time-resolved fluorescence upconversion studies on polydiacetylene derivatives.