Vibrational dynamics of a perylene-perylenediimide donor-acceptor dyad probed with femtosecond stimulated Raman spectroscopy

Kristen E. Brown, Brad S. Veldkamp, Dick T Co, Michael R Wasielewski

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)2362-2366
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume3
Issue number17
DOIs
Publication statusPublished - Sep 6 2012

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Perylene
Excited states
Anions
Raman spectroscopy
Charge transfer
vibration mode
Negative ions
charge transfer
anions
vibration
dynamic structural analysis
Photoexcitation
Structural dynamics
polarization (charge separation)
photoexcitation
Discrete Fourier transforms
Ground state
Stretching
excitation
ground state

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Vibrational dynamics of a perylene-perylenediimide donor-acceptor dyad probed with femtosecond stimulated Raman spectroscopy. / Brown, Kristen E.; Veldkamp, Brad S.; Co, Dick T; Wasielewski, Michael R.

In: Journal of Physical Chemistry Letters, Vol. 3, No. 17, 06.09.2012, p. 2362-2366.

Research output: Contribution to journalArticle

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AB - 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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