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  Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state

Chatterjee, G., Jha, A., Blanco-Gonzalez, A., Tiwari, V., Manathunga, M., Duan, H.-G., et al. (2022). Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state. Chemical Science, 13(32), 9392-9400. doi:10.1039/D2SC02133A.

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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. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by ab initio molecular dynamics simulations. Mapping the potential energy landscape attributes the observed charge-coupled coherent nuclear motions to the population of the initial segment of a double-bond isomerization channel, also seen in biological molecules. Our results illustrate the pivotal role of pre-twisted molecular geometries in enhancing the transfer of vibrational energy to specific molecular modes, prior to thermal redistribution. This motivates the search for synthetic strategies towards achieving potentially new infrared-mediated chemistry.

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Language(s): eng - English
 Dates: 2022-04-132022-07-192022-07-192022-08-28
 Publication Status: Issued
 Pages: 9
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/D2SC02133A
 Degree: -

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Project name : The experimental work was funded by the Max-Planck- Gesellscha. The authors acknowledge Prof. Nils Huse (University of Hamburg) and the Sample Preparation and Characterization (SPC) Facility of EMBL Hamburg for access to their FTIR spectrometers and Dr Stephan Niebling (EMBL Hamburg) for assistance with the FTIR measurements. The authors further thank Djordje Gitaric, Hendrik Schikora and Jan-Philipp Leimkohl (MPSD) for technical support, Dr Shree- tama Karmakar (TIFR) for initial discussions and Dr Michal Kochman (MPSD) for preliminary simulations. M.O. is grateful to the National Science Foundation for grant no. CHE-1710191, for a MIUR Department of Excellence Grant 2018–2022 and to the Fondazione Banca d'Italia and the Ohio Supercomputer Center for the provided computational facilities and services.
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Title: Chemical Science
  Other : Chem. Sci.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 13 (32) Sequence Number: - Start / End Page: 9392 - 9400 Identifier: ISSN: 2041-6520
CoNE: https://pure.mpg.de/cone/journals/resource/2041-6520