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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. 

Abstract The formation and evolution of post-solitons has been discussed for quite some time both analytically and through the use of particle-in-cell (PIC) codes. It is however only recently that they have been directly observed in laser-plasma experiments. Relativistic electromagnetic (EM) solitons are localised structures that can occur in collisionless plasmas. They consist of a low-frequency EM wave trapped in a low electron number-density cavity surrounded by a shell with a higher electron number-density. Here we describe the results of an experiment in which a 100 TW Ti:sapphire laser (30 fs, 800 nm) irradiates a $0.03\mathrm{g}\mathrm{c}{\mathrm{m}}^{-3}$TMPTA foam target with a focused intensity $I_{\mathrm{l}}=9.5\times {10}^{17}\mathrm{W}\mathrm{c}{\mathrm{m}}^{-2}$. A third harmonic ( ${\lambda }_{\mathrm{p}\mathrm{r}\mathrm{o}\mathrm{b}\mathrm{e}}\simeq 266$nm) probe is employed to diagnose plasma motion for 25 ps after the main pulse interaction via Doppler-Spectroscopy. Both radiation-hydrodynamics and 2D PIC simulations are performed to aid in the interpretation of the experimental results. We show that the rapid motion of the probe critical-surface observed in the experiment might be a signature of post-soliton wall motion.