title: Two-Dimensional Vibrational Spectroscopy of a Dissipative System with the Optimized Mean-Trajectory Approximation.
abstract: The optimized mean-trajectory (OMT) approximation is a semiclassical method for computing vibrational response functions from action-quantized classical trajectories connected by discrete transitions representing radiation-matter interactions. Here we apply this method to an anharmonic chromophore coupled to a harmonic bath. A forward-backward trajectory implementation of the OMT method is described that addresses the numerical challenges of applying the OMT to large systems with disparate frequency scales. The OMT is shown to well reproduce line shapes and waiting time dynamics in the pure dephasing limit of weak coupling to an off-resonant bath. The OMT is also shown to describe a case where energy transfer is the predominant source of line broadening.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States.
authors.forename: Mallory
authors.initials: M
authors.lastname: Alemi
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States.
authors.forename: Roger F
authors.initials: RF
authors.lastname: Loring
mesh_terms: D008956:Models, Chemical; D013057:Spectrum Analysis; D014732:Vibration