Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state.
Gourab ChatterjeeAjay JhaAlejandro Blanco-GonzálezVandana TiwariMadushanka ManathungaHong-Guang DuanFriedjof TellkampValentyn I ProkhorenkoNicolas FerréJyotishman DasguptaMassimo OlivucciR J Dwyane MillerPublished in: Chemical science (2022)
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.
Keyphrases
- molecular dynamics simulations
- energy transfer
- solar cells
- molecular docking
- high resolution
- single molecule
- quantum dots
- high glucose
- drug discovery
- diabetic rats
- living cells
- solid state
- human health
- single cell
- drug induced
- high density
- cerebral ischemia
- climate change
- transition metal
- endothelial cells
- tissue engineering