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Acceleration of a ground-state reaction by selective femtosecond-infrared-laser-pulse excitation

Nature Chemistry volume 10, pages 126131 (2018) | Download Citation

Abstract

Infrared (IR) excitation of vibrations that participate in the reaction coordinate of an otherwise thermally driven chemical reaction are believed to lead to its acceleration. Attempts at the practical realization of this concept have been hampered so far by competing processes leading to sample heating. Here we demonstrate, using femtosecond IR-pump IR-probe experiments, the acceleration of urethane and polyurethane formation due to vibrational excitation of the reactants for 1:1 mixtures of phenylisocyanate and cyclohexanol, and toluene-2,4-diisocyanate and 2,2,2-trichloroethane-1,1-diol, respectively. We measured reaction rate changes upon selective vibrational excitation with negligible heating of the sample and observed an increase of the reaction rate up to 24%. The observation is rationalized using reactant and transition-state structures obtained from quantum chemical calculations. We subsequently used IR-driven reaction acceleration to write a polyurethane square on sample windows using a femtosecond IR pulse.

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Acknowledgements

The work was supported by the Deutsche Forschungsgemeinschaft (grants nos Ku952/6 and He5206/3, CRC 1078 ‘Protonation Dynamics in Protein Function’, Project B07, CRC 1114 ‘Scaling Cascades in Complex Systems’, Project B05). The authors thank N.P. Ernsting for discussions and the group of S. Reich for Raman microscopy experiments.

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Affiliations

  1. Department of Physics, Freie Universität Berlin, Arnimallee 14, 14195 Berlin, Germany

    • Till Stensitzki
    • , Yang Yang
    • , Valeri Kozich
    • , Florian Kössl
    •  & Karsten Heyne
  2. Faculty of Science, Department of Chemistry, University of Cairo, 12613 Giza, Egypt

    • Ashour A. Ahmed
  3. Institute of Physics, University of Rostock, Albert Einstein-Strasse 23-24, 18059 Rostock, Germany

    • Ashour A. Ahmed
    •  & Oliver Kühn

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Contributions

T.S. performed the femtosecond experiments on CH-ol and PHI, analysed the data and contributed to writing the paper. Y.Y. performed the femtosecond experiments on CH-ol and PHI. V.K. performed acceleration measurements, photolithography measurements, analysed the data and contributed to writing the paper. F.K. provided the samples. A.A.A. performed the quantum chemical calculations, analysed their results and contributed to writing the paper. K.H. and O.K. contributed to all measurements, calculations and analysis and wrote the paper. All authors commented on the manuscript.

Competing interests

V.K., F.K. and K.H. are listed as inventors on a patent application describing infrared-light-induced yield optimization of chemical reactions. These patents are pending in the EU (EP2014056220) and the USA (US 2016/0051963). K.H. is also listed on a patent describing a method for polymerizing monomer units and/or oligomer units by means of infrared light pulses. This patent includes US patent no. 1412448 and EU patent no. EP 2718005. The other authors declare no competing financial interests.

Corresponding author

Correspondence to Karsten Heyne.

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DOI

https://doi.org/10.1038/nchem.2909

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