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  Vibrational Excitation Initiates Biomimetic Charge-Coupled Motions in the Electronic Ground State

Chatterjee, G., Jha, A., Blanco-Gonzalez, A., Tiwari, V., Manathunga, M., Duan, H.-G., et al. (2020). Vibrational Excitation Initiates Biomimetic Charge-Coupled Motions in the Electronic Ground State. doi:10.26434/chemrxiv.13270469.v1.

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vibrational-excitation-initiates-biomimetic-charge-coupled-motions-in-the-electronic-ground-state.pdf (Preprint), 5MB
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vibrational-excitation-initiates-biomimetic-charge-coupled-motions-in-the-electronic-ground-state.pdf
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 Creators:
Chatterjee, G.1, Author              
Jha, A.1, Author              
Blanco-Gonzalez, A.2, Author
Tiwari, V.1, 3, Author              
Manathunga, M.2, Author
Duan, H.-G.1, Author              
Tellkamp, F.4, Author              
Prokhorenko, V.1, Author              
Ferré, N.5, Author
Dasgupta, J.6, Author
Olivucci, M.2, 7, Author
Miller, R. J. D.8, Author
Affiliations:
1Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938288              
2Department of Chemistry, Bowling Green State University, ou_persistent22              
3Department of Chemistry, University of Hamburg, ou_persistent22              
4Machine Physics, Scientific Service Units, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2074322              
5Aix-Marseille Univ, CNRS, ICR, ou_persistent22              
6Department of Chemical Sciences, Tata Institute of Fundamental Research, ou_persistent22              
7Dipartimento di Biotechnologie, Chimica e Farmacia, Università di Siena, ou_persistent22              
8Departments of Chemistry and Physics, University of Toronto, ou_persistent22              

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 Abstract: The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Manipulating reaction pathways to achieve product selectivity via precise control of light-molecule interactions has allured chemists for decades. Yet it remains an elusive challenge in the electronic ground state, where conventional thermally-driven chemistry occurs. Here, we demonstrate that ground-state vibrational excitation of localised bridge modes initiates charge transfer in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change in the ground-state electronic configuration is visualised by transient absorption spectroscopy, involving a mid-infrared pump and a visible probe, and detailed ab initio molecular dynamics simulations. Mapping the potential energy landscape unravels a hitherto undocumented charge-transfer-assisted double-bond isomerization channel in the electronic ground state. The reaction pathway bears remarkable parallels with the thermal isomerization process in rhodopsin, the retinal protein responsible for scotopic vision. Our results illustrate a generic protocol for activating key vibrational modes to drive photo-triggered ground-state reactions and motivate synthetic and catalytic strategies to achieving potentially new chemistry.

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Language(s): eng - English
 Dates: 2020-11-23
 Publication Status: Published online
 Pages: 36
 Publishing info: -
 Table of Contents: -
 Rev. Type: No review
 Identifiers: DOI: 10.26434/chemrxiv.13270469.v1
 Degree: -

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