ja505387c_si_001.pdf (2.21 MB)
Photorelaxation Induced by Water–Chromophore Electron Transfer
journal contribution
posted on 2014-07-23, 00:00 authored by Mario BarbattiRelaxation of photoexcited chromophores
is a key factor determining
diverse molecular properties, from luminescence to photostability.
Radiationless relaxation usually occurs through state intersections
caused by distortions in the nuclear geometry of the chromophore.
Using excited-state nonadiabatic dynamics simulations based on algebraic
diagrammatic construction, it is shown that this is the case of 9H-adenine
in water cluster, but not of 7H-adenine in water cluster. 7H-adenine
in water cluster relaxes via a state intersection induced by electron
transfer from water to the chromophore. This result reveals an unknown
reaction pathway, with implications for the assignment of relaxation
mechanisms of exciton relaxation in organic electronics. The observation
of photorelaxation of 7H-adenine induced by water–chromophore
electron transfer is a proof of principle calling for further computational
and experimental investigations to determine how common this effect
is.