Two-Dimensional Electronic-Vibrational Spectroscopy

Multidimensional non-linear spectroscopies, in the infrared and electronic (see 2DES) 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 non-radiative relaxation pathways of select dye molecules in solution, the electronic-vibrational dynamics of biomimetic systems, and the coherent energy transfer dynamics of novel nanostructures and molecules with strong electronic coupling (see Center for Synthesizing Quantum Coherence), as well as natural photosynthetic systems.

In addition to experimental investigations, we have performed theoretical calculations that simulate the 2DEV spectra of model systems that mimic light-harvesting complexes. We use a near-analytical approach to understand the role that a vibrational mode, resonant with the energy gap between a pair of excitons, plays in the excitation energy transport dynamics and the related signatures in the 2DEV spectra.

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

Contact: Shiun-Jr Yang

Helpful Background Reading:

1. Two-dimensional Fourier transform electronic spectroscopy. JD Hybl, A Albrecht Ferro, DM Jonas, J Chem Phys, 115, 6606–6622 (2001).

2. Phase-stabilized two-dimensional electronic spectroscopy. T Brixner, T Mancal, IV Stiopkin, GR Fleming, J Chem Phys, 121, 4221–4236 (2004).

3. Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems. GS Engel, TR Calhoun, EL Read, et al., Nature, 446, 782–786 (2001).

4. Optical 2-D Fourier Transform Spectroscopy of Excitons in Semiconductor Nanostructures. ST Cundiff, AD Bristow, M Siemens, et al., IEEE J Select Topics Quantum Electron, 18, 318–328 (2012).

5. Reaction dynamics of a molecular switch unveiled by coherent two-dimensional electronic spectroscopy. M Kullmann, S Ruetzel, J Buback, et al. J Am Chem Soc, 133,13074–13080 (2011).

6. Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time. J Zheng, K Kwak, J Asbury, et al., Science, 309, 1338–1343 (2005).

7. From the Cover: Multidimensional Ultrafast Spectroscopy Special Feature: Two-dimensional spectroscopy at infrared and optical frequencies. RM Hochstrasser, Proc Natl Acad Sci USA, 104, 14190–14196 (2007).

8. Coherent two-dimensional optical spectroscopy. M Cho, Chem Rev, 108,1331–1418 (2008).

9. Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy. TAA Oliver, NHC Lewis, GR Fleming, Proc Natl Acad Sci USA, 111,10061–10066 (2014).

10. Automated 2D IR spectroscopy using a mid-IR pulse shaper and application of this technology to the human islet amyloid polypeptide. S-H Shim, DB Strasfeld, YL Ling, MT Zanni, Proc Natl Acad Sci USA, 104, 14197–14202 (2007).

11. Two-color two-dimensional Fourier transform electronic spectroscopy with a pulse-shaper. JA Myers, KLM Lewis, PF Tekavec, JP Ogilvie, Opt Express, 16, 17420–17428 (2008).