Kristen Brown - Vibrational Dynamics of a Perylene–Perylenediimide Donor–Acceptor Dyad Probed with Femtosecond Stimulated Raman Spectroscopy

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      Brown, K. E.; Veldkamp, B. S.; Co, D. T.; Wasielewski, M. R.,   Vibrational Dynamics of a Perylene–Perylenediimide Donor–Acceptor   Dyad Probed with Femtosecond Stimulated Raman Spectroscopy. J.   Phys. Chem. Lett. 2012, 2362-2366.


        The ultrafast vibrational dynamics of the photoinduced   charge-transfer reaction between perylene (Per) and   perylene-3,4:9,10-bis(dicarboximide) (PDI) were investigated   using femtosecond stimulated Raman spectroscopy (FSRS).   Specifically probing the structural dynamics of PDI following its   selective photoexcitation in a covalently linked dyad reveals   vibrational modes uniquely characteristic to the PDI lowest   excited singlet state and radical anion between 1000 and 1700   cm–1.   A comparison of these vibrations to those of the ground state   reveals the appearance of new   1*PDI   and PDI–•    stretching modes in the dyad at 1593 and 1588   cm–1,   respectively. DFT calculations reveal that these vibrations are   parallel to the long axis of PDI and thus then may be integral to   the charge separation reaction. The ability to differentiate   excited state from radical anion vibrational modes allows the   evaluation of the influence of specific modes on the charge   transfer dynamics in donor–bridge–acceptor systems based on PDI   molecular constructs.

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