Dissecting hidden couplings using fifth-order three-dimensional electronic spectroscopy

Andrew F. Fidler, Elad Harel, Gregory S. Engel

Research output: Contribution to journalArticlepeer-review

47 Scopus citations


We report the demonstration of single-quantum 3D electronic spectroscopy. Utilizing the recently introduced gradient assisted photon echo (GRAPE) methodology, the fifth-order nonlinear polarization of the solvatochromatic dye IR144 corresponding to evolution through three sequential single-quantum coherences is measured. GRAPE, which allows a 2D slice of data to be acquired in parallel, permits a practical implementation of 3D spectroscopy at optical frequencies in a matter of minutes instead of hours. By spreading frequencies into a third spectral dimension, we can resolve features in the spectra that are otherwise obscured. For IR144, a previously unresolved cross peak originating from high frequency vibronic modes is observed in the spectrum. Theoretical modeling based on the cumulant expansion truncated at second order reproduces the main features of the experimental results. This experimental approach will enable further high dimensional spectroscopic experiments.

Original languageEnglish (US)
Pages (from-to)2876-2880
Number of pages5
JournalJournal of Physical Chemistry Letters
Issue number19
StatePublished - Oct 7 2010

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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