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Quantum interference between H + D2 quasiclassical reaction mechanisms

Nature Chemistry volume 7, pages 661–667 (2015)Cite this article

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Abstract

Interferences are genuine quantum phenomena that appear whenever two seemingly distinct classical trajectories lead to the same outcome. They are common in elastic scattering but are seldom observable in chemical reactions. Here we report experimental measurements of the state-to-state angular distribution for the H + D2 reaction using the ‘photoloc’ technique. For products in low rotational and vibrational states, a characteristic oscillation pattern governs backward scattering. The comparison between the experiments, rigorous quantum calculations and classical trajectories on an accurate potential energy surface allows us to trace the origin of that structure to the quantum interference between different quasiclassical mechanisms, a phenomenon analogous to that observed in the double-slit experiment.

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Figure 1: Comparison between experimental and theoretically simulated angular distributions for H + D2  HD(v′ = 1, j′) + D at a mean collision energy of 1.97 eV.
Figure 2: Comparison between experimental and theoretically simulated angular distributions for H + D2  HD(v′ = 3, j′) + D at an average collision energy of 1.97 eV.
Figure 3: Interpretation of the classical deflection function for the H + D2(v = 0, j = 0) HD(v′ = 1, j′ = 0) + D reaction at Ecoll = 1.97 eV.
Figure 4: Origin of multiple peaks in backward scattering of HD(v′ = 1, j′ = 0, 3, 5) products.
Figure 5: The interference between different classical mechanisms that scatter at the same angle causes the multiple peaks observed in the experimental DCSs for HD(v′ = 1, j′ = 0).
Figure 6: Coherences between different groups of partial waves for HD(v′ = 3, j′ = 0, 1) products.

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Acknowledgements

The authors acknowledge funding by the Spanish Ministry of Economy and Competitiveness (grants CTQ2012-37404-C02 and Consolider Ingenio 2010 CSD2009–00038) and the US National Science Foundation (CHE-1151428).

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  1. Justinas Jankunas: Deceased. This paper is dedicated to his memory

Authors and Affiliations

  1. Departamento de Química Física I, Facultad de Química, Universidad Complutense de Madrid, Madrid, 28040, Spain

    Pablo G. Jambrina, Diego Herráez-Aguilar & F. Javier Aoiz

  2. Department of Chemistry, Stanford University, Stanford, 94305-5080, California, USA

    Mahima Sneha, Justinas Jankunas & Richard N. Zare

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  1. Pablo G. Jambrina
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  5. Justinas Jankunas
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Contributions

R.N.Z. and F.J.A. conceived and designed the research. M.S. and J.J. conducted the photoloc technique experiments, and P.G.J. and D.H.A. carried out the QM and QCT calculations. P.G.J., F.J.A. and R.N.Z. wrote the paper, with contributions from all co-authors.

Corresponding authors

Correspondence to F. Javier Aoiz or Richard N. Zare.

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The authors declare no competing financial interests.

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Jambrina, P., Herráez-Aguilar, D., Aoiz, F. et al. Quantum interference between H + D2 quasiclassical reaction mechanisms. Nature Chem 7, 661–667 (2015). https://doi.org/10.1038/nchem.2295

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