Vibrational coherences in half-broadband 2D electronic spectroscopy: Spectral filtering to identify excited state displacements

Green, Dale ORCID:, Bressan, Giovanni ORCID:, Heisler, Ismael A., Meech, Stephen R. ORCID: and Jones, Garth A. (2024) Vibrational coherences in half-broadband 2D electronic spectroscopy: Spectral filtering to identify excited state displacements. The Journal of Chemical Physics, 160 (23). ISSN 0021-9606

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Vibrational coherences in ultrafast pump-probe (PP) and 2D electronic spectroscopy (2DES) provide insights into the excited state dynamics of molecules. Femtosecond coherence spectra and 2D beat maps yield information about displacements of excited state surfaces for key vibrational modes. Half-broadband 2DES uses a PP configuration with a white light continuum probe to extend the detection range and resolve vibrational coherences in the excited state absorption (ESA). However, the interpretation of these spectra is difficult as they are strongly dependent on the spectrum of the pump laser and the relative displacement of the excited states along the vibrational coordinates. We demonstrate the impact of these convoluting factors for a model based upon cresyl violet. A careful consideration of the position of the pump spectrum can be a powerful tool in resolving the ESA coherences to gain insights into excited state displacements. This paper also highlights the need for caution in considering the spectral window of the pulse when interpreting these spectra.

Item Type: Article
Additional Information: Data availability: The data that support the findings of this study are openly available in Zenodo at Funding information: Engineering and Physical Sciences Research Council under Award No. EP/V00817X/1.
Uncontrolled Keywords: 2d electronic spectroscopy;,beat maps,2d efemtosecond coherence spectra,vibrational coherence,physics and astronomy(all),physical and theoretical chemistry,sdg 7 - affordable and clean energy ,/dk/atira/pure/subjectarea/asjc/3100
Faculty \ School: Faculty of Science > School of Physics
Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Faculty of Science > Research Groups > Chemistry of Light and Energy
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Depositing User: LivePure Connector
Date Deposited: 25 Jun 2024 10:30
Last Modified: 10 Jul 2024 01:53
DOI: 10.1063/5.0214023


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