Coherent population transfer in molecules coupled with a dissipative environment by an intense ultrashort chirped pulse

We have studied the intense chirped pulse excitation of a molecule coupled with a dissipative environment taking into account electronic coherence effects. We considered a two-state electronic system with relaxation treated as a diffusion on electronic potential energy surfaces. This relaxation model enables us to trace continuously the transition from a coherent population transfer to incoherent one. An inhomogeneously broadened system with frozen nuclear motion is invoked to model a purely coherent transfer. We show that the type of population transfer ~coherent or incoherent! strongly depends on the pulse chirp, its sign, and the detunings of the exciting pulse carrier frequency with respect to the frequency of the Franck-Condon transition. For positive chirped pulses and moderate detunings, relaxation does not hinder a coherent population transfer. Moreover, under these conditions the relaxation favors more efficient population transfer with respect to the ‘‘coherent’’ system with frozen nuclear motion. © 2002 American Institute of Physics. @DOI: 10.1063/1.1505869#