Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state - Aix-Marseille Université Access content directly
Journal Articles Chemical Science Year : 2022

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

Gourab Chatterjee
Ajay Jha
Alejandro Blanco-Gonzalez
Vandana Tiwari
Madushanka Manathunga
  • Function : Author
Hong-Guang Duan
  • Function : Author
Friedjof Tellkamp
  • Function : Author
Valentyn Prokhorenko
  • Function : Author
Nicolas Ferré
Jyotishman Dasgupta
Massimo Olivucci
R. Miller

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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hal-03818171 , version 1 (10-01-2024)

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Attribution - NonCommercial

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Gourab Chatterjee, Ajay Jha, Alejandro Blanco-Gonzalez, Vandana Tiwari, Madushanka Manathunga, et al.. Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state. Chemical Science, 2022, 13 (32), pp.9392-9400. ⟨10.1039/d2sc02133a⟩. ⟨hal-03818171⟩
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