Spectral Filtering as a Tool for Two-Dimensional Spectroscopy: A Theoretical Model.

ABSTRACT

Two-dimensional optical spectroscopy is a powerful technique for the probing of coherent quantum superpositions. Recently, the finite width of the laser spectrum has been employed to selectively tune experiments for the study of particular coherences. This involves the exclusion of certain transition frequencies, which results in the elimination of specific Liouville pathways. The rigorous analysis of such experiments requires the use of ever more sophisticated theoretical models for the optical spectroscopy of electronic and vibronic systems. Here we develop a nonimpulsive and non-Markovian model, which combines an explicit definition of the laser spectrum, via the equation of motion-phase matching approach (EOM-PMA), with the hierarchical equations of motion (HEOM). This theoretical framework is capable of simulating the 2D spectroscopy of vibronic systems with low frequency modes, coupled to environments of intermediate and slower time scales. In order to demonstrate the spectral filtering of vibronic coherences, we examine the elimination of lower energy peaks from the 2D spectra of a zinc porphyrin monomer upon blue-shifting the laser spectrum. The filtering of Liouville pathways is revealed through the disappearance of peaks from the amplitude spectra for a coupled vibrational mode.