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Revealing the stereospecific chemistry of the reaction of Cl with aligned CHD3(ν1 = 1)

Nature Chemistry volume 4, pages 636–641 (2012)Cite this article

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Abstract

The concept of geometrical constraints and steric hindrance in reactions is implanted deeply in a chemist's ‘chemical intuition’. However, until now a true three-dimensional view of these steric effects has not been realized experimentally for any chemical reaction in full. Here we report the complete three-dimensional characterization of the sterics of a benchmark polyatomic reaction by measuring the dependence of the product state-resolved angular distributions on the spatial alignment of the reactive bond in a crossed molecular beam experiment. The results prove the existence of two distinct microscopic reaction mechanisms. Detailed analysis reveals that the origin of the stereodynamics in the HCl(ν = 0) + CD3(00) product channel can be captured by a textbook line-of-centres collision model. In contrast, a time-delay pathway, which includes a sharp switch from in-plane to out-of-plane scattering in the forwards direction, appears to be operative in forming the excited HCl(ν = 1) + CD3(00) product pair.

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Figure 1: Schematic representation of the experimental set-up and scattering coordinate for data analysis.
Figure 2: Three normalized raw images at Ec = 3.8 kcal mol−1 for infrared laser polarization (the red double arrows) directed along three orthogonal axes (x, y and z).
Figure 3: Pair-correlated angular distributions observed in the xz scattering plane for infrared laser polarization pointing along the three orthogonal axes x, y and z.
Figure 4: Comparison of the experimentally determined PDDCS with the predictions from a LOC model, and a 3D visualization of how the reaction proceeds.

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Acknowledgements

We thank J-S. Lin and C-M. Yang for assisting with the experiment. K.L. acknowledges M.P. de Miranda and F.J. Aoiz for clarifying the angular asymmetry of S1+2(θ). This work was supported by the National Science Council of Taiwan, Academia Sinica and the Air Force Office of Scientific Research (Grant No. AOARD-12-4020).

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Authors and Affiliations

  1. Institute of Atomic and Molecular Sciences, Academia Sinica, P.O. Box 23-166, Taipei, 10617, Taiwan

    Fengyan Wang & Kopin Liu

  2. Department of Chemistry, National Tsing Hua University, Hsinchu, 300, Taiwan

    Kopin Liu

  3. Department of Physics, National Taiwan University, Taipei, 10617, Taiwan

    Kopin Liu

  4. Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, Heraklion-Crete, 71110, Greece

    T. Peter Rakitzis

  5. Department of Physics, University of Crete, Heraklion-Crete, 71003, Greece

    T. Peter Rakitzis

Authors
  1. Fengyan Wang
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Contributions

K.L. conceived and designed the experiments and F.W. performed the experiments and analysed the data. F.W., T.P.R. and K.L. contributed to the analysis methods, discussed the results and commented on the manuscript. K.L. wrote the paper.

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Correspondence to Kopin Liu.

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The authors declare no competing financial interests.

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Wang, F., Liu, K. & Rakitzis, T. Revealing the stereospecific chemistry of the reaction of Cl with aligned CHD3(ν1 = 1). Nature Chem 4, 636–641 (2012). https://doi.org/10.1038/nchem.1383

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