Vibrational Dephasing along the Reaction Coordinate of an Electron Transfer Reaction

Yusuke Yoneda, Bryan Kudisch, Shahnawaz Rafiq, Margherita Maiuri, Yutaka Nagasawa, Gregory D. Scholes, Hiroshi Miyasaka

Research output: Contribution to journalArticlepeer-review

Abstract

The role of molecular vibration in photoinduced electron transfer (ET) reactions has been extensively debated in recent years. In this study, we investigated vibrational wavepacket dynamics in a model ET system consisting of an organic dye molecule as an electron acceptor dissolved in various electron donating solvents. By using broad band pump-probe (BBPP) spectroscopy with visible laser pulses of sub-10 fs duration, coherent vibrational wavepackets of naphthacene dye with frequencies spanning 170-1600 cm-1were observed in the time domain. The coherence properties of 11 vibrational modes were analyzed by an inverse Fourier filtering procedure, and we discovered that the dephasing times of some vibrational coherences are reduced with increasing ET rates. Density functional theory calculations indicated that the corresponding vibrational modes have a large Huang-Rhys factor between the reactant and the product states, supporting the hypothesis that the loss of phase coherence along certain vibrational modes elucidates that those vibrations are coupled to the reaction coordinate of an ET reaction.

Original languageEnglish (US)
Pages (from-to)14511-14522
Number of pages12
JournalJournal of the American Chemical Society
Volume143
Issue number36
DOIs
StatePublished - Sep 15 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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