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How can infra-red excitation both accelerate and slow charge transfer in the same molecule?

Publication ,  Journal Article
Ma, Z; Lin, Z; Lawrence, CM; Rubtsov, IV; Antoniou, P; Skourtis, SS; Zhang, P; Beratan, DN
Published in: Chemical science
August 2018

A UV-IR-Vis 3-pulse study of infra-red induced changes to electron transfer (ET) rates in a donor-bridge-acceptor species finds that charge-separation rates are slowed, while charge-recombination rates are accelerated as a result of IR excitation during the reaction. We explore the underpinning mechanisms for this behavior, studying IR-induced changes to the donor-acceptor coupling, to the validity of the Condon approximation, and to the reaction coordinate distribution. We find that the dominant IR-induced rate effects in the species studied arise from changes to the density of states in the Marcus curve crossing region. That is, IR perturbation changes the probability of accessing the activated complex for the ET reactions. IR excitation diminishes the population of the activated complex for forward (activationless) ET, thus slowing the rate. However, IR excitation increases the population of the activated complex for (highly activated) charge recombination ET, thus accelerating the charge recombination rate.

Duke Scholars

Published In

Chemical science

DOI

EISSN

2041-6539

ISSN

2041-6520

Publication Date

August 2018

Volume

9

Issue

30

Start / End Page

6395 / 6405

Related Subject Headings

  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Ma, Z., Lin, Z., Lawrence, C. M., Rubtsov, I. V., Antoniou, P., Skourtis, S. S., … Beratan, D. N. (2018). How can infra-red excitation both accelerate and slow charge transfer in the same molecule? Chemical Science, 9(30), 6395–6405. https://doi.org/10.1039/c8sc00092a
Ma, Zheng, Zhiwei Lin, Candace M. Lawrence, Igor V. Rubtsov, Panayiotis Antoniou, Spiros S. Skourtis, Peng Zhang, and David N. Beratan. “How can infra-red excitation both accelerate and slow charge transfer in the same molecule?Chemical Science 9, no. 30 (August 2018): 6395–6405. https://doi.org/10.1039/c8sc00092a.
Ma Z, Lin Z, Lawrence CM, Rubtsov IV, Antoniou P, Skourtis SS, et al. How can infra-red excitation both accelerate and slow charge transfer in the same molecule? Chemical science. 2018 Aug;9(30):6395–405.
Ma, Zheng, et al. “How can infra-red excitation both accelerate and slow charge transfer in the same molecule?Chemical Science, vol. 9, no. 30, Aug. 2018, pp. 6395–405. Epmc, doi:10.1039/c8sc00092a.
Ma Z, Lin Z, Lawrence CM, Rubtsov IV, Antoniou P, Skourtis SS, Zhang P, Beratan DN. How can infra-red excitation both accelerate and slow charge transfer in the same molecule? Chemical science. 2018 Aug;9(30):6395–6405.
Journal cover image

Published In

Chemical science

DOI

EISSN

2041-6539

ISSN

2041-6520

Publication Date

August 2018

Volume

9

Issue

30

Start / End Page

6395 / 6405

Related Subject Headings

  • 34 Chemical sciences
  • 03 Chemical Sciences