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

Green, Dale, Valduga de Almeida Camargo, Franco, Heisler, Ismael A., Dijkstra, Arend G. and Jones, Garth A. (2018) Spectral Filtering as a Tool for Two-Dimensional Spectroscopy: A Theoretical Model. The Journal of Physical Chemistry A, 122 (30). 6206–6213. ISSN 1089-5639

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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 non-impulsive 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 timescales. In order to demonstrate the spectral filtering of vibronic coherences, we examine the elimination of lower energy peaks fromthe 2D spectra of a zinc porphyrin monomer on 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.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: Pure Connector
Date Deposited: 18 Jul 2018 14:26
Last Modified: 12 Jun 2021 09:45
URI: https://ueaeprints.uea.ac.uk/id/eprint/67649
DOI: 10.1021/acs.jpca.8b03339

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