Observing Vibrational Wavepackets during an Ultrafast Electron Transfer Reaction

Shahnawaz Rafiq, Jacob C. Dean, Gregory D. Scholes

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Recent work has proposed that coherent effects impact ultrafast electron transfer reactions. Here we report studies using broadband pump-probe and two-dimensional electronic spectroscopy of intramolecular nuclear motion on the time scale of the electron transfer between oxazine 1 (Ox1) and dimethylaniline (DMA). We performed time-frequency analysis on the time domain data to assign signal amplitude modulations to ground or excited electronic states in the reactive system (Ox1 in DMA) relative to the control system (Ox1 in chloronaphthalene). It was found that our ability to detect vibrational coherence via the excited electronic state of Ox1 diminishes on the time scale that population is lost by electron transfer. However, the vibrational wavepacket is not damped by the electron transfer process and has been observed previously by detecting the Ox1 radical transient absorption. The analysis presented here indicates that the "addition" of an electron to the photoexcited electron acceptor does not significantly perturb the vibrational coherence, suggesting its presence as a spectator, consistent with the Born-Oppenheimer separation of electronic and nuclear degrees of freedom.

Original languageEnglish (US)
Pages (from-to)11837-11846
Number of pages10
JournalJournal of Physical Chemistry A
Volume119
Issue number49
DOIs
StatePublished - Dec 10 2015

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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