- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Letters

Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Featured in Physics
  • Editors' Suggestion
  • Open Access

Fast Molecular Compression by a Hyperthermal Collision Gives Bond-Selective Mechanochemistry

Lukas Krumbein1,†, Kelvin Anggara1,†, Martina Stella2, Tomasz Michnowicz1, Hannah Ochner1, Sabine Abb1, Gordon Rinke1, André Portz3, Michael Dürr3 et al.

Uta Schlickum1,4, Andrew Baldwin5, Andrea Floris6, Klaus Kern1,7, and Stephan Rauschenbach1,5,*

  • 1Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, DE-70569 Stuttgart, Germany
  • 2Department of Materials, Royal School of Mines, Imperial College London, Exhibition Road, London SW7 2A2, United Kingdom
  • 3Institut für Angewandte Physik, Justus-Liebig-Universität Giessen, Heinrich-Buff-Ring 16, DE-35392 Giessen, Germany
  • 4Institut für Angewandte Physik, Technische Universität Braunschweig, Mendelssohnstrasse 2, DE-38106 Braunschweig, Germany
  • 5Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, United Kingdom
  • 6School of Chemistry, University of Lincoln, Brayford Pool, Lincoln LN6 7TS, United Kingdom
  • 7Institut de Physique, École Polytechnique Fédérale de Lausanne, Laussane CH-1015, Switzerland

  • *Corresponding Author. stephan.rauschenbach@chem.ox.ac.uk
  • †L. K. and K. A. contributed equally to this work.
PDF

Phys. Rev. Lett. 126, 056001 – Published 1 February, 2021

DOI: https://doi.org/10.1103/PhysRevLett.126.056001

Abstract

Using electrospray ion beam deposition, we collide the complex molecule Reichardt’s dye (C41H30NO+) at low, hyperthermal translational energy (2–50 eV) with a Cu(100) surface and image the outcome at single-molecule level by scanning tunneling microscopy. We observe bond-selective reaction induced by the translational kinetic energy. The collision impulse compresses the molecule and bends specific bonds, prompting them to react selectively. This dynamics drives the system to seek thermally inaccessible reactive pathways, since the compression timescale (subpicosecond) is much shorter than the thermalization timescale (nanosecond), thereby yielding reaction products that are unobtainable thermally.

View figure in article

Physics Subject Headings (PhySH)

Viewpoint

Selective Bond Breaking with Splat Chemistry

Published 1 February, 2021

Colliding a large organic molecule with a surface can break a specific chemical bond in the molecule with surprising precision.

See more in Physics

Article Text

Supplemental Material

References (63)

  1. S. T. Ceyer, Science 249, 133 (1990).
  2. H. Hou, S. J. Gulding, C. T. Rettner, A. M. Wodtke, and D. J. Auerbach, Science 277, 80 (1997).
  3. R. D. Beck, P. Maroni, D. C. Papageorgopoulos, T. T. Dang, M. P. Schmid, and T. R. Rizzo, Science 302, 98 (2003).
  4. R. R. Smith, D. R. Killelea, D. F. DelSesto, and A. L. Utz, Science 304, 992 (2004).
  5. D. R. Killelea, V. L. Campbell, N. S. Shuman, and A. L. Utz, Science 319, 790 (2008).
  6. B. L. Yoder, R. Bisson, and R. D. Beck, Science 329, 553 (2010).
  7. L. Chen, H. Ueta, R. Bisson, and R. D. Beck, Faraday Discuss. 157, 285 (2012).
  8. X. J. Shen, A. Lozano, W. Dong, H. F. Busnengo, and X. H. Yan, Phys. Rev. Lett. 112, 046101 (2014).
  9. B. Jiang, M. Yang, D. Xie, and H. Guo, Chem. Soc. Rev. 45, 3621 (2016).
  10. D. C. Jacobs, Annu. Rev. Phys. Chem. 53, 379 (2002).
  11. J. V. Barth, G. Costantini, and K. Kern, Nature (London) 437, 671 (2005).
  12. G. Dubey, R. Urcuyo, S. Abb, G. Rinke, M. Burghard, S. Rauschenbach, and K. Kern, J. Am. Chem. Soc. 136, 13482 (2014).
  13. A. R. Dongré, Á. Somogyi, and V. H. Wysocki, J. Mass Spectrom. 31, 339 (1996).
  14. V. Grill, J. Shen, C. Evans, and R. G. Cooks, Rev. Sci. Instrum. 72, 3149 (2001).
  15. J. Laskin, T. H. Bailey, and J. H. Futrell, J. Am. Chem. Soc. 125, 1625 (2003).
  16. X. Ma, M. Zhou, and V. H. Wysocki, J. Am. Soc. Mass Spectrom. 25, 368 (2014).
  17. S. R. Harvey, J. T. Seffernick, R. S. Quintyn, Y. Song, Y. Ju, J. Yan, A. N. Sahasrabuddhe, A. Norris, M. Zhou, E. J. Behrman, S. Lindert, and V. H. Wysocki, Proc. Natl. Acad. Sci. U.S.A. 116, 8143 (2019).
  18. F. F. Crim, Proc. Natl. Acad. Sci. U.S.A. 105, 12654 (2008).
  19. H. Guo and B. Jiang, Acc. Chem. Res. 47, 3679 (2014).
  20. B. D. Kay, T. D. Raymond, and M. E. Coltrin, Phys. Rev. Lett. 59, 2792 (1987).
  21. K. Golibrzuch, J. H. Baraban, P. R. Shirhatti, J. Werdecker, C. Bartels, and A. M. Wodtke, Z. Phys. Chem. 229, 1929 (2015).
  22. J. A. Burroughs, S. B. Wainhaus, and L. Hanley, J. Phys. Chem. 98, 10913 (1994).
  23. R. D. Beck, J. Rockenberger, P. Weis, and M. M. Kappes, J. Chem. Phys. 104, 3638 (1996).
  24. W. R. Koppers, J. H. M. Beijersbergen, K. Tsumori, T. L. Weeding, P. G. Kistemaker, and A. W. Kleyn, Phys. Rev. B 53, 11207 (1996).
  25. J. R. Morris, G. Kim, T. L. O. Barstis, R. Mitra, and D. C. Jacobs, J. Chem. Phys. 107, 6448 (1997).
  26. Y. Yao, P. Shushkov, T. F. Miller, and K. P. Giapis, Nat. Commun. 10, 2294 (2019).
  27. S. Rauschenbach, M. Ternes, L. Harnau, and K. Kern, Annu. Rev. Anal. Chem. 9, 473 (2016).
  28. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevLett.126.056001 for full experimental and calculation details, which includes Refs. [29–49].
  29. V. G. Machado, R. I. Stock, and C. Reichardt, Chem. Rev. 114, 10429 (2014).
  30. J. Tersoff and D. R. Hamann, Phys. Rev. Lett. 50, 1998 (1983).
  31. J. Tersoff and D. R. Hamann, Phys. Rev. B 31, 805 (1985).
  32. L. N. Kantorovich (1996) User-friendly visualisation program for ab initio DFT codes vasp, siesta, qe, and quickstep, https://nms.kcl.ac.uk/lev.kantorovitch/codes/lev00/index.html.
  33. G. Kresse and J. Hafner, Phys. Rev. B 47, 558 (1993).
  34. G. Kresse and J. Furthmüller, Phys. Rev. B 54, 11169 (1996).
  35. P. E. Blöchl, Phys. Rev. B 50, 17953 (1994).
  36. S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, J. Chem. Phys. 132, 154104 (2010).
  37. K. Momma and F. Izumi, J. Appl. Crystallogr. 44, 1272 (2011).
  38. F. Neese, Comput. Mol. Sci. 2, 73 (2012).
  39. F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297 (2005).
  40. J. Zheng, X. Xu, and D. G. Truhlar, Theor. Chem. Acc. 128, 295 (2011).
  41. I. L. Geada, H. Ramezani-Dakhel, T. Jamil, M. Sulpizi, and H. Heinz, Nat. Commun. 9, 716 (2018).
  42. G. L. Stoychev, A. A. Auer, and F. Neese, J. Chem. Theory Comput. 13, 554 (2017).
  43. H. Jónsson, G. Mills, and K. W. Jacobsen, Nudged elastic band method for finding minimum energy paths transitions, in Classical and Quantum Dynamics in Condensed Phase Simulations, edited by B. J. Berne, G. Ciccotti, and D. F. Coker (World Scientific, Singapore, 1998), p. 385.
  44. G. Henkelman, B. P. Uberuaga, and H. Jónsson, J. Chem. Phys. 113, 9901 (2000).
  45. P. Giannozzi et al., J. Phys. Condens. Matter 21, 395502 (2009).
  46. G. Kresse and D. Joubert, Phys. Rev. B 59, 1758 (1999).
  47. J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).
  48. R. Sabatini, T. Gorni, and S. de Gironcoli, Phys. Rev. B 87, 041108(R) (2013).
  49. M. Methfessel and A. T. Paxton, Phys. Rev. B 40, 3616 (1989).
  50. J. J. Gilman, Science 274, 65 (1996).
  51. H. Yan, F. Yang, D. Pan, Y. Lin, J. N. Hohman, D. Solis-Ibarra, F. H. Li, J. E. P. Dahl, R. M. K. Carlson, B. A. Tkachenko, A. A. Fokin, P. R. Schreiner, G. Galli, W. L. Mao, Z.-X. Shen, and N. A. Melosh, Nature (London) 554, 505 (2018).
  52. E. Kolodney, A. Amirav, R. Elber, and R. B. Gerber, Chem. Phys. Lett. 111, 366 (1984).
  53. H. A. Michelsen, C. T. Rettner, D. J. Auerbach, and R. N. Zare, J. Chem. Phys. 98, 8294 (1993).
  54. R. D. Levine, Molecular Reaction Dynamics (Cambridge University Press, Cambridge, 2005).
  55. J. C. Polanyi and R. J. Wolf, Ber. Bunsenges. Phys. Chem. 86, 356 (1982).
  56. J. C. Polanyi and R. J. Wolf, J. Chem. Phys. 82, 1555 (1985).
  57. K. D. Rendulic and A. Winkler, Surf. Sci. 299–300, 261 (1994).
  58. L. Leung, T. Lim, Z. Ning, and J. C. Polanyi, J. Am. Chem. Soc. 134, 9320 (2012).
  59. H. Lesnard, M.-L. Bocquet, and N. Lorente, J. Am. Chem. Soc. 129, 4298 (2007).
  60. J. N. Ladenthin, T. Frederiksen, M. Persson, J. C. Sharp, S. Gawinkowski, J. Waluk, and T. Kumagai, Nat. Chem. 8, 935 (2016).
  61. N. Bartels, K. Golibrzuch, C. Bartels, L. Chen, D. J. Auerbach, A. M. Wodtke, and T. Schäfer, Proc. Natl. Acad. Sci. U.S.A. 110, 17738 (2013).
  62. K. H. Kramer and R. B. Bernstein, J. Chem. Phys. 42, 767 (1965).
  63. http://www.archer.ac.uk

Outline

Information

Phys. Rev. Lett. 126, 056001– Published 1 February, 2021
  • Received 14 July 2020
  • Accepted 7 December 2020
Crossmark - Check for updates button
Creative Commons Logo

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI. Open access publication funded by the Max Planck Society.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation