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Femtosecond characterization of vibrational optical activity of chiral molecules

Nature volume 458, pages 310–313 (2009)Cite this article

Abstract

Optical activity1,2,3 is the result of chiral molecules interacting differently with left versus right circularly polarized light. Because of this intrinsic link to molecular structure, the determination of optical activity through circular dichroism (CD) spectroscopy has long served as a routine method for obtaining structural information about chemical and biological systems in condensed phases4,5,6. A recent development is time-resolved CD spectroscopy, which can in principle map the structural changes associated with biomolecular function7 and thus lead to mechanistic insights into fundamental biological processes. But implementing time-resolved CD measurements is experimentally challenging because CD is a notoriously weak effect (a factor of 10-4–10-6 smaller than absorption). In fact, this problem has so far prevented time-resolved vibrational CD experiments. Here we show that vibrational CD spectroscopy with femtosecond time resolution can be realized when using heterodyned spectral interferometry to detect8,9,10 the phase and amplitude of the infrared optical activity free-induction-decay field in time (much like in a pulsed NMR experiment). We show that we can detect extremely weak signals in the presence of large achiral background contributions, by simultaneously measuring with a femtosecond laser pulse the vibrational CD and optical rotatory dispersion spectra of dissolved chiral limonene molecules. We have so far only targeted molecules in equilibrium, but it would be straightforward to extend the method for the observation of ultrafast structural changes such as those occurring during protein folding or asymmetric chemical reactions. That is, we should now be in a position to produce ‘molecular motion pictures’11 of fundamental molecular processes from a chiral perspective.

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Figure 1: Heterodyned detection of optical activity free induction decay.
Figure 2: Vibrational optical activity signals of chiral limonenes.

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Acknowledgements

This work was supported by Creative Research Initiatives (CMDS) of MEST/KOSEF (M.C.) and the Frontier Research Laboratory Program of KBSI (S.-J.J.).

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Authors and Affiliations

  1. Department of Chemistry,,

    Hanju Rhee, Young-Gun June, Jang-Soo Lee, Kyung-Koo Lee, Zee Hwan Kim, Seung-Joon Jeon & Minhaeng Cho

  2. Center for Multidimensional Spectroscopy, Korea University, Seoul 136-701, Korea,

    Hanju Rhee, Jang-Soo Lee, Kyung-Koo Lee & Minhaeng Cho

  3. Multidimensional Spectroscopy Laboratory, Korea Basic Science Institute, Seoul 136-713, Korea

    Jeong-Hyon Ha, Seung-Joon Jeon & Minhaeng Cho

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  1. Hanju Rhee
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Correspondence to Minhaeng Cho.

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Rhee, H., June, YG., Lee, JS. et al. Femtosecond characterization of vibrational optical activity of chiral molecules. Nature 458, 310–313 (2009). https://doi.org/10.1038/nature07846

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