Monitoring the evolution of intersite and interexciton coherence in electronic excitation transfer via wave-packet interferometry.

We detail an experimental strategy for tracking the generation and time-development of electronic coherence within the singly excited manifold of an energy-transfer dimer. The technique requires that the two monomers have nonparallel electronic transition-dipole moments and that these possess fixed orientations in space. It makes use of two-dimensional wave-packet interferometry (WPI or whoopee) measurements in which the A, B, C, and D pulses have respective polarizations e, e, e, and e'. In the case of energy-transfer coupling that is weak or strong compared to electronic-nuclear interactions, it is convenient to follow the evolution of intersite or interexciton coherence, respectively. Under weak coupling, e could be perpendicular to the acceptor chromophore's transition dipole moment and the unit vector e' would be perpendicular to the donor's transition dipole. Under strong coupling, e could be perpendicular to the ground-to-excited transition dipole to the lower exciton level and e' would be perpendicular to the ground-to-excited transition dipole to the upper exciton level. If the required spatial orientation can be realized for an entire ensemble, experiments of the kind proposed could be performed by either conventional four-wave-mixing or fluorescence-detected WPI methods. Alternatively, fluorescence-detected whoopee experiments of this kind could be carried out on a single energy-transfer dimer of fixed orientation. We exhibit detailed theoretical expressions for the desired WPI signal, explain the physical origin of electronic coherence detection, and show calculated observed-coherence signals for model dimers with one, two, or three internal vibrational modes per monomer and both weak and strong energy-transfer coupling.