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.; Tellkamp, F.; Prokhorenko, V.; Ferré, N.; Dasgupta, J.; Olivucci, M.; Miller, R. J. D.

doi:10.1039/D2SC02133A

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Journal Article

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

MPS-Authors

Chatterjee, G.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

Jha, A.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Tiwari, V.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Department of Chemistry, University of Hamburg;
International Max Planck Research School for Ultrafast Imaging & Structural Dynamics (IMPRS-UFAST), Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

Duan, H.-G.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

Tellkamp, F.
Machine Physics, Scientific Service Units, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

Prokhorenko, V.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

External Resource

https://doi.org/10.1039/D2SC02133A
(Publisher version)

https://doi.org/10.26434/chemrxiv.13270469.v1
(Preprint)

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d2sc02133a.pdf
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d2sc02133a1.pdf
(Supplementary material), 7MB

Citation

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.

Cite as: https://hdl.handle.net/21.11116/0000-000A-DEB8-D

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.