Vibrational modes are often localized in certain regions of a molecule, and so the coupling between these modes is sensitive to the molecular structure. Two-dimensional vibrational spectroscopy can probe the strength of this coupling in a manner analogous to two-dimensional NMR spectroscopy, but on ultrafast timescales. Here, we demonstrate how two-dimensional Raman spectroscopy, based on fifth-order optical nonlinearity, can be performed with a single beam of shaped femtosecond optical pulses. Our spectroscopy scheme offers not only a major simplification of the conventional set-up, but also an inherent elimination of a competing nonlinear signal, which overwhelms the desired signal in other schemes and carries no coupling information.
Subscribe to Journal
Get full journal access for 1 year
only $14.08 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Hybl, J. D., Albrecht Ferro, A. & Jonas, D. M. Two-dimensional Fourier transform electronic spectroscopy. J. Chem. Phys. 115, 6606–6622 (2001).
Brixner, T. et al. Two-dimensional spectroscopy of electronic couplings in photosynthesis. Nature 434, 625–628 (2005).
Tian, P., Keusters, D., Suzaki, Y. & Warren, W. S. Femtosecond phase-coherent two-dimensional spectroscopy. Science 300, 1553–1555 (2003).
Grumstrup, E. M., Shim, S. H., Montgomery, M. A., Damrauer, N. H. & Zanni, M. T. Facile collection of two-dimensional electronic spectra using femtosecond pulse-shaping technology. Opt. Express 15, 16681–16690 (2007).
Hornung, T., Vaughan, J. C., Feurer, T. & Nelson, K. A. Degenerate four-wave mixing spectroscopy based on two-dimensional femtosecond pulse shaping. Opt. Lett. 29, 2052–2054 (2004).
Molesky, B. P., Giokas, P. G., Guo, Z. & Moran, A. M. Multidimensional resonance Raman spectroscopy by six-wave mixing in the deep UV. J. Chem. Phys. 141, 114202 (2014).
Glenn, R. & Mukamel, S. Multidimensional spectroscopy with a single broadband phase-shaped laser pulse. J. Chem. Phys. 140, 144105 (2014).
Baiz, C. R., Schach, D. & Tokmakoff, A. Ultrafast 2D IR microscopy. Opt. Express 22, 18724–18735 (2014).
Kolano, C., Helbing, J., Kozinski, M., Sander, W. & Hamm, P. Watching hydrogen-bond dynamics in a beta-turn by transient two-dimensional infrared spectroscopy. Nature 444, 469–472 (2006).
Asplund, M. C., Zanni, M. T. & Hochstrasser, R. M. Two-dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes. Proc. Natl Acad. Sci. USA 97, 8219–8224 (2000).
Krummel, A. T. & Zanni, M. T. DNA vibrational coupling revealed with two-dimensional infrared spectroscopy: insight into why vibrational spectroscopy is sensitive to DNA structure. J. Phys. Chem. B 110, 13991–14000 (2006).
Fayer, M. D. Fast protein dynamics probed with infrared vibrational echo experiments. Annu. Rev. Phys. Chem. 52, 315–356 (2001).
Tanimura, Y. & Mukamel, S. Two-dimensional femtosecond vibrational spectroscopy of liquids. J. Chem. Phys. 99, 9496–9511 (1993).
Tokmakoff, A., Lang, M. J., Larsen, D. S. & Fleming, G. R. Two-dimensional Raman spectroscopy of vibrational interactions in liquids. Phys. Rev. Lett. 79, 2702–2705 (1997).
Blank, D. A., Kaufman, L. J. & Fleming, G. R. Direct fifth-order electronically nonresonant Raman scattering from CS2 at room temperature. J. Chem. Phys. 113, 771–778 (2000).
Mukamel, S., Piryatinski, A. & Chernyak, V. Two-dimensional Raman echoes: femtosecond view of molecular structure and vibrational coherence. Acc. Chem. Res. 32, 145–154 (1999).
Okumura, K., Tokmakoff, A. & Tanimura, Y. Structural information from two-dimensional fifth-order Raman spectroscopy. J. Chem. Phys. 111, 492–503 (1999).
Ulness, D. J., Kirkwood, J. C. & Albrecht, A. C. Competitive events in fifth order time resolved coherent Raman scattering: direct versus sequential processes. J. Chem. Phys. 108, 3897–3902 (1998).
Blank, D. A., Kaufman, L. J. & Fleming, G. R. Fifth-order two-dimensional Raman spectra of CS2 are dominated by third-order cascades. J. Chem. Phys. 111, 3105–3114 (1999).
Wilson, K. C., Lyons, B., Mehlenbacher, R., Sabatini, R. & McCamant, D. W. Two-dimensional femtosecond stimulated Raman spectroscopy: observation of cascading Raman signals in acetonitrile. J. Chem. Phys. 131, 214502 (2009).
Dudovich, N., Oron, D. & Silberberg, Y. Single-pulse coherently controlled nonlinear Raman spectroscopy and microscopy. Nature 418, 512–514 (2002).
Dudovich, N., Oron, D. & Silberberg, Y. Single-pulse coherent anti-Stokes Raman spectroscopy in the fingerprint spectral region. J. Chem. Phys. 118, 9208–9215 (2003).
Jang, H. U. et al. Interaction of a finite train of short pulses with an atomic ladder system. Phys. Rev. A 82, 043424 (2010).
Pestov, D., Lozovoy, V. V. & Dantus, M. Multiple independent comb shaping (MICS): phase-only generation of optical pulse sequences. Opt. Express 17, 14351–14361 (2009).
Frostig, H., Katz, O., Natan, A. & Silberberg, Y. Single-pulse stimulated Raman scattering spectroscopy. Opt. Lett. 36, 1248–1250 (2011).
Duarte, M. F. & Eldar, Y. C. Structured compressed sensing: from theory to applications. IEEE Trans. Signal Process. 59, 4053–4085 (2011).
Eldar, Y. C., Kuppinger, P. & Bolcskei, H. Block-sparse signals: uncertainty relations and efficient recovery. IEEE Trans. Signal Process. 58, 3042–3054 (2010).
Kaufman, L. J., Blank, D. A. & Fleming, G. R. Polarization selectivity in fifth-order electronically nonresonant Raman scattering from CS2 . J. Chem. Phys. 114, 2312–2331 (2001).
Golonzka, O., Demirdoven, N., Khalil, M. & Tokmakoff, A. Separation of cascaded and direct fifth-order Raman signals using phase-sensitive intrinsic heterodyne detection. J. Chem. Phys. 113, 9893–9896 (2000).
Cho, M. et al. Intrinsic cascading contributions to the fifth- and seventh-order electronically off-resonant Raman spectroscopies. J. Chem. Phys. 112, 2082–2094 (2000).
Astinov, V., Kubarych, K. J., Milne, C. J. & Miller, R. J. D. Diffractive optics based two-color six-wave mixing: phase contrast heterodyne detection of the fifth order Raman response of liquids. Chem. Phys. Lett. 327, 334–342 (2000).
Dunbar, J. A., Osborne, D. G., Anna, J. M. & Kubarych, K. J. Accelerated 2D-IR using compressed sensing. J. Phys. Chem. Lett. 4, 2489–2492 (2013).
The authors thank B. Bruner and L. Chuntonov for useful discussions. This work was supported by Icore (Israeli centres of research excellence of the ISF), the Crown Photonics Center, the Wolfson Foundation and the European ICT project FAMOS.
The authors declare no competing financial interests.
About this article
Cite this article
Frostig, H., Bayer, T., Dudovich, N. et al. Single-beam spectrally controlled two-dimensional Raman spectroscopy. Nature Photon 9, 339–343 (2015). https://doi.org/10.1038/nphoton.2015.64
Physical Review X (2020)
The Journal of Chemical Physics (2020)
Optics Express (2020)
The Journal of Chemical Physics (2020)
Signatures of Intra- and Intermolecular Vibrational Coupling in Halogenated Liquids Revealed by Two-Dimensional Raman-Terahertz Spectroscopy
The Journal of Physical Chemistry Letters (2019)