Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state. Issue 32 (4th August 2022)

• Record Type: Journal Article
• Authors: Chatterjee, Gourab; Jha, Ajay; Blanco-Gonzalez, Alejandro; Tiwari, Vandana; Manathunga, Madushanka; Duan, Hong-Guang; Tellkamp, Friedjof; Prokhorenko, Valentyn I.; Ferré, Nicolas; Dasgupta, Jyotishman; Olivucci, Massimo; Miller, R. J. Dwayne
• Is Part Of: Chemical science. Volume 13:Issue 32(2022)
• Page Start: 9392
• Page End: 9400
• Publication Date: 2022-08-04
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc02133a
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Channelling vibrational excitation energy to achieve ground-state charge-transfer (CT)-assisted isomerization in a donor-bridge-acceptor molecule in solution. 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.