Two-dimensional vibrational-electronic spectra with semiclassical mechanics

Two-dimensional vibrational-electronic (2DVE) spectra probe the effects on vibronic spectra of initial vibrational excitation in an electronic ground state. The optimized mean trajectory (OMT) approximation is a semiclassical method for computing nonlinear spectra from response functions. Ensembles of classical trajectories are subject to semiclassical quantization conditions, with the radiation-matter interaction inducing discontinuous transitions. This approach has been previously applied to two-dimensional infrared and electronic spectra and is extended here to 2DVE spectra. For a system including excitonic coupling, vibronic coupling, and interaction of a chromophore vibration with a resonant environment, the OMT method is shown to well approximate exact quantum dynamics.

Automated summary

The optimized mean trajectory (OMT) approximation is a semiclassical method for studying vibrational-electronic (2DVE) spectra in a bimolecular system, and it can approximate exact quantum dynamics well. This method has previously been applied to two-dimensional infrared and electronic spectra, and has been extended to the study of 2DVE spectra.