<p>The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Manipulating reaction pathways to
achieve product selectivity via precise control of light-molecule interactions
has allured chemists for decades. Yet it remains an elusive challenge in the
electronic ground state, where conventional thermally-driven chemistry occurs. Here, we demonstrate that
ground-state vibrational excitation of localised bridge modes initiates charge
transfer in a donor-bridge-acceptor molecule in solution. The
vibrationally-induced change in the ground-state electronic configuration is
visualised by transient absorption spectroscopy, involving a mid-infrared pump
and a visible probe, and detailed <i>ab initio </i>molecular dynamics simulations. Mapping the potential
energy landscape unravels a hitherto undocumented charge-transfer-assisted
double-bond isomerization channel in the electronic ground state. The reaction
pathway bears remarkable parallels with the thermal isomerization process in
rhodopsin, the retinal protein responsible for scotopic vision. Our results
illustrate a generic protocol for activating key vibrational modes to drive
photo-triggered ground-state reactions and motivate synthetic and catalytic
strategies to achieving potentially new chemistry. </p>
Temperature‐Dependent Electronic Ground‐State Charge Transfer in van der Waals Heterostructures
