2D Electronic-Vibrational Spectroscopy

Multidimensional non-linear spectroscopies, in the infrared and electronic (see 2D-ES) domains have become mature experimental techniques to study electronic relaxation and energy transfer dynamics of molecules, nanomaterials and biological molecules, [1-5] vibrational couplings and ground state structures of chemical and biological systems.[6-8] To date, the advantages of these two experimental techniques have never been combined, as to directly correlate the electronic and vibrational degrees of freedom simultaneously. We have developed two-dimensional electronic-vibrational spectroscopy (2DEV); a new experimental tool to probe photo-biochemical dynamics [9]. We take advantage of techniques routinely used in NMR, such as phase cycling, and perform 2DEV experiments in a partially collinear geometry, as recently used in 2D infrared and electronic spectroscopies [10, 11]. The 2DEV technique will be used to explore the electronic-vibrational dynamics of dye molecules in solution, the complex non-radiative pathways of carotenoids and electron-phonon coupling in nanomaterials (see electronic-vibrational coupling).

2DEV SetupSchematic experimental 2DEV setup. Inset spectra displays 2DEV spectrum for DCM in DMSO-d6 solution (see [9]).


Helpful Background Reading:

  1. Hybl JD, Albrecht Ferro A, Jonas DM (2001) Two-dimensional Fourier transform electronic spectroscopy. J Chem Phys 115:6606–6622.
  2. Brixner T, Mancal T, Stiopkin IV, Fleming GR (2004) Phase-stabilized two-dimensional electronic spectroscopy. J Chem Phys 121:4221–4236.
  3. Engel GS, Calhoun TR, Read EL, et al. (2007) Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems. Nature 446:782–786.
  4. Cundiff ST, Bristow AD, Siemens M, et al. (2012) Optical 2-D Fourier Transform Spectroscopy of Excitons in Semiconductor Nanostructures. IEEE J Select Topics Quantum Electron 18:318–328.
  5. Kullmann M, Ruetzel S, Buback J, et al. (2011) Reaction dynamics of a molecular switch unveiled by coherent two-dimensional electronic spectroscopy. J Am Chem Soc 133:13074–13080.
  6. Zheng J, Kwak K, Asbury J, et al. (2005) Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time. Science 309:1338–1343.
  7. Hochstrasser RM (2007) From the Cover: Multidimensional Ultrafast Spectroscopy Special Feature: Two-dimensional spectroscopy at infrared and optical frequencies. Proc Natl Acad Sci USA 104:14190–14196.
  8. Cho M (2008) Coherent two-dimensional optical spectroscopy. Chem Rev 108:1331–1418.
  9. Oliver TAA, Lewis NHC, Fleming GR (2014) Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy. Proc Natl Acad Sci USA 111:10061–10066.[PDF].
  10. Shim S-H, Strasfeld DB, Ling YL, Zanni MT (2007) Automated 2D IR spectroscopy using a mid-IR pulse shaper and application of this technology to the human islet amyloid polypeptide. Proc Natl Acad Sci USA 104:14197–14202.
  11. Myers JA, Lewis KLM, Tekavec PF, Ogilvie JP (2008) Two-color two-dimensional Fourier transform electronic spectroscopy with a pulse-shaper. Opt Express 16:17420–17428.