Lattice dynamics from the ‘eyes’ of the chromophore Real-time studies of I₂ isolated in rare gas matrices

Abstract

Molecular iodine isolated in rare gas solids is used as a model system to develop the framework for interpretation of condensed phase pump–probe observables, specializing in information content regarding multi-body dynamics. The principles are illustrated through a series of examples, where, beside the molecular vibronic coherence, the cage motions can be directly dissected. The large variety of behaviors which can be staged in this system include: elastic cage recoil, highly non-linear and dissipative cage response, long-lived cage coherence driven through guest–host resonances, nearly decoupled guest–host dynamics, and cage induced dynamical solvation of electronic surfaces. Although the underlying dynamics can be understood in great depth when aided by simulations, we attempt a clear distinction between direct experimental observables and inferences based on simulations.

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