Intermolecular interaction dynamics and optical dephasing: Picosecond photon echo measurements in mixed molecular crystals

Abstract

Picosecond optical coherence techniques are employed to study dynamical intermolecular interactions in low concentration mixed molecular crystals, i.e., pentacene in naphthalene at 1.4 K. A concentration‐dependent broadening of the optical homogeneous line is observed. Stimulated photon echo measurements rule out excited state transport as the broadening mechanism. The photon echo results exhibit a linear concentration dependence and a theory is proposed that accounts for the broadening in terms of phonon‐induced fluctuations in guest–guest dipole–dipole interactions. Detailed considerations indicate that the system is best described in terms of localized excitations rather than delocalized impurity band states. In the low concentration limit, there is additional broadening of the homogeneous line beyond that produced by the lifetime. A model is presented describing this broadening in terms of phonon‐induced modulation of the guest–host van der Waals interactions, i.e., in terms of a fluctuating crystal shift.