Two-dimensional electronic spectroscopy resolves relative excited-state displacements

Bressan, Giovanni ORCID: https://orcid.org/0000-0001-7801-8495, Green, Dale ORCID: https://orcid.org/0000-0002-2549-0486, Jones, Garth A., Heisler, Ismael A. and Meech, Stephen R. ORCID: https://orcid.org/0000-0001-5561-2782 (2024) Two-dimensional electronic spectroscopy resolves relative excited-state displacements. The Journal of Physical Chemistry Letters, 15 (10). pp. 2876-2884. ISSN 1948-7185

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Abstract

Knowledge of relative displacements between potential energy surfaces (PES) is critical in spectroscopy and photochemistry. Information on displacements is encoded in vibrational coherences. Here we apply ultrafast two-dimensional electronic spectroscopy in a pump−probe half-broadband (HB2DES) geometry to probe the ground- and excited-state potential landscapes of cresyl violet. 2D coherence maps reveal that while the coherence amplitude of the dominant 585 cm−1 Raman-active mode is mainly localized in the ground- state bleach and stimulated emission regions, a 338 cm−1 mode is enhanced in excited-state absorption. Modeling these data with a three-level displaced harmonic oscillator model using the hierarchical equation of motion-phase matching approach (HEOM-PMA) shows that the S1 ← S0 PES displacement is greater along the 585 cm−1 coordinate than the 338 cm−1 coordinate, while Sn ← S1 displacements are similar along both coordinates. HB2DES is thus a powerful tool for exploiting nuclear wavepackets to extract quantitative multidimensional, vibrational coordinate information across multiple PESs.

Item Type: Article
Additional Information: Acknowledgements: The simulations presented in this letter were carried out on the High Performance Computing Cluster supported by the Research and Specialist Computing Support service at the University of East Anglia. We acknowledge support from the Engineering and Physical Sciences Research Council under award no. EP/V00817X/1.
Uncontrolled Keywords: spectroscopy,physical and theoretical chemistry,sdg 7 - affordable and clean energy ,/dk/atira/pure/subjectarea/asjc/1600/1607
Faculty \ School: Faculty of Science > School of Chemistry
Faculty of Science > School of Physics
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: 14 Mar 2024 14:30
Last Modified: 21 Mar 2024 09:30
URI: https://ueaeprints.uea.ac.uk/id/eprint/94691
DOI: 10.1021/acs.jpclett.3c03420

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