Vibrational Funnels for Energy Transfer in Organic Chromophores

Photoinducedintramolecular energy transfers in multichromophoricmolecules involve nonadiabatic vibronic channels that act as energytransfer funnels. They commonly take place through specific directionsof motion dictated by the nonadiabatic coupling vectors. Vibrationalfunnels may support persistent coherences between electronic statesand sometimes delineate the presence of minor alternative energy transferpathways. The ultimate confirmation of their role on the interchromophoricenergy transfer can be achieved by performing nonadiabatic excited-statemolecular dynamics simulations by selectively freezing the nuclearmotions in question. Our results point out this strategy as a usefultool to identify and evaluate the impact of these vibrational funnelson the energy transfer processes and guide the in silico design ofmaterials with tunable properties and enhanced functionalities. Ourwork encourages applications of this methodology to different chemicaland biochemical processes such as reactive scattering and proteinconformational changes, to name a few.

Automated summary

Photoinduced intramolecular energy transfers in multichromophoric molecules occur through specific motion directions guided by nonadiabatic coupling vectors, forming energy transfer funnels. Vibrational funnels can support persistent coherences between electronic states and reveal minor energy transfer pathways. Nonadiabatic excited-state molecular dynamics simulations with frozen nuclear motions can confirm the role of vibrational funnels in interchromophoric energy transfer. Our work highlights the usefulness of this strategy in identifying and evaluating the impact of vibrational funnels on energy transfer processes and guiding the design of materials with tunable properties and enhanced functionalities. Furthermore, we encourage the application of this methodology to various chemical and biochemical processes, such as reactive scattering and protein conformational changes.