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Absolute excited state molecular geometries revealed by resonance Raman signals

Author

Listed:
  • Giovanni Batignani

    (Sapienza Universitá di Roma
    Istituto Italiano di Tecnologia, Center for Life Nano Science @Sapienza)

  • Emanuele Mai

    (Sapienza Universitá di Roma
    Istituto Italiano di Tecnologia, Center for Life Nano Science @Sapienza)

  • Giuseppe Fumero

    (Sapienza Universitá di Roma)

  • Shaul Mukamel

    (University of California)

  • Tullio Scopigno

    (Sapienza Universitá di Roma
    Istituto Italiano di Tecnologia, Center for Life Nano Science @Sapienza
    Istituto Italiano di Tecnologia, Graphene Labs)

Abstract

Ultrafast reactions activated by light absorption are governed by multidimensional excited-state (ES) potential energy surfaces (PESs), which describe how the molecular potential varies with the nuclear coordinates. ES PESs ad-hoc displaced with respect to the ground state can drive subtle structural rearrangements, accompanying molecular biological activity and regulating physical/chemical properties. Such displacements are encoded in the Franck-Condon overlap integrals, which in turn determine the resonant Raman response. Conventional spectroscopic approaches only access their absolute value, and hence cannot determine the sense of ES displacements. Here, we introduce a two-color broadband impulsive Raman experimental scheme, to directly measure complex Raman excitation profiles along desired normal modes. The key to achieve this task is in the signal linear dependence on the Frank-Condon overlaps, brought about by non-degenerate resonant probe and off-resonant pump pulses, which ultimately enables time-domain sensitivity to the phase of the stimulated vibrational coherences. Our results provide the tool to determine the magnitude and the sensed direction of ES displacements, unambiguously relating them to the ground state eigenvectors reference frame.

Suggested Citation

  • Giovanni Batignani & Emanuele Mai & Giuseppe Fumero & Shaul Mukamel & Tullio Scopigno, 2022. "Absolute excited state molecular geometries revealed by resonance Raman signals," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-35099-3
    DOI: 10.1038/s41467-022-35099-3
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    References listed on IDEAS

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    1. Dario Polli & Piero Altoè & Oliver Weingart & Katelyn M. Spillane & Cristian Manzoni & Daniele Brida & Gaia Tomasello & Giorgio Orlandi & Philipp Kukura & Richard A. Mathies & Marco Garavelli & Giulio, 2010. "Conical intersection dynamics of the primary photoisomerization event in vision," Nature, Nature, vol. 467(7314), pages 440-443, September.
    2. Rocío Borrego-Varillas & Artur Nenov & Piotr Kabaciński & Irene Conti & Lucia Ganzer & Aurelio Oriana & Vishal Kumar Jaiswal & Ines Delfino & Oliver Weingart & Cristian Manzoni & Ivan Rivalta & Marco , 2021. "Tracking excited state decay mechanisms of pyrimidine nucleosides in real time," Nature Communications, Nature, vol. 12(1), pages 1-7, December.
    3. Giovanni Batignani & Giuseppe Fumero & Ajay Ram Srimath Kandada & Giulio Cerullo & Marina Gandini & Carino Ferrante & Annamaria Petrozza & Tullio Scopigno, 2018. "Probing femtosecond lattice displacement upon photo-carrier generation in lead halide perovskite," Nature Communications, Nature, vol. 9(1), pages 1-5, December.
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