The selective excitation of molecular vibrations provides a means to directly influence the speed and outcome of chemical reactions. Such mode-selective chemistry1 has traditionally used laser pulses to prepare reactants in specific vibrational states2 to enhance reactivity3,4 or modify the distribution of product species5,6. Inelastic tunnelling electrons may also excite molecular vibrations7,8 and have been used to that effect on adsorbed molecules, to cleave individual chemical bonds9 and induce molecular motion10,11,12,13 or dissociation14,15,16,17. Here we demonstrate that inelastic tunnelling electrons can be tuned to induce selectively either the translation or desorption of individual ammonia molecules on a Cu(100) surface. We are able to select a particular reaction pathway by adjusting the electronic tunnelling current and energy during the reaction induction such that we activate either the stretching vibration of ammonia or the inversion of its pyramidal structure. Our results illustrate the ability of the scanning tunnelling microscope to probe single-molecule events in the limit of very low yield and very low power irradiation, which should allow the investigation of reaction pathways not readily amenable to study by more conventional approaches.
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Jortner, J., Levine, R. D. & Pullman, B. (eds) Mode Selective Chemistry (Kluwer Academic, Dordrecht, 1991)
Dai, H. L. & Ho, W. (eds) Laser Spectroscopy and Photochemistry on Metal Surfaces (World Scientific, Singapore, 1995)
Higgings, J., Conjusteau, A., Scoles, G. & Bernasek, S. L. State selective vibrational (2ν3) activation of the chemisorption of methane on Pt(111). J Chem. Phys. 114, 5277–5283 (2001)
Potter, E. D., Herek, J. L., Pedersen, S., Liu, Q. & Zewail, A. H. Femtosecond laser control of a chemical reaction. Nature 355, 66–68 (1992)
Sinha, A., Hsiao, M. C. & Crim, F. F. Controlling bimolecular reactions: Mode and bond selected reaction of water with hydrogen atoms. J. Chem. Phys. 94, 4928–4935 (1991)
Bronikowski, M. J., Simpson, W. R., Girard, B. & Zare, R. N. Bond-specific chemistry: OD:OH product ratios for the reactions H + HOD(100) and H + HOD(001). J. Chem. Phys. 95, 8647–8648 (1991)
Hansma, P. K. (ed.) Tunnelling Spectroscopy: Capabilities, Applications, and New Techniques (Plenum, New York, 1982)
Stipe, B. C., Rezaei, M. A. & Ho, W. Single-molecule vibrational spectroscopy and microscopy. Science 280, 1732–1735 (1998)
Ho, W. Inducing and viewing bond selected chemistry with tunneling electrons. Acc. Chem. Res. 31, 567–573 (1998)
Eigler, D. M., Lutz, C. P. & Rudge, W. E. An atomic switch realized with the scanning tunnelling microscope. Nature 352, 600–603 (1991)
Stipe, B. C., Rezai, M. A. & Ho, W. Coupling of vibrational excitation to the rotational motion of a single adsorbed molecule. Phys. Rev. Lett. 81, 1263–1266 (1998)
Komeda, T., Kim, Y., Kawai, M., Persson, B. N. J. & Ueba, H. Lateral hopping of molecules induced by excitation of internal vibration mode. Science 295, 2055–2058 (2002)
Bartels, L. et al. Atomic scale chemistry: Desorption of ammonia from Cu(111) induced by tunneling electrons. Chem. Phys. Lett. 313, 544–552 (1999)
Avouris, Ph. Manipulation of matter at the atomic and molecular level. Acc. Chem. Res. 28, 95–102 (1995)
Stipe, B. C. et al. Single-molecule dissociation by tunneling electrons. Phys. Rev. Lett. 78, 4410–4413 (1997)
Hla, S. W., Bartels, L., Meyer, G. & Rieder, K. H. Inducing all steps of a chemical reaction with the scanning tunneling microscope tip: Towards single molecule engineering. Phys. Rev. Lett. 85, 2777–2780 (2000)
Kim, Y., Komeda, T. & Kawai, M. Single-molecule reaction and characterization by vibrational excitation. Phys. Rev. Lett. 89, 126104 (2002)
Rust, H.-P., Buisset, J., Schweizer, E. K. & Cramer, L. High precision mechanical approach mechanism for a low temperature scanning tunneling microscope. Rev. Sci. Instrum. 68, 129–132 (1997)
Hertel, T., Wolf, M. & Ertl, G. UV photostimulated desorption of ammonia from Cu(111). J. Chem. Phys. 102, 3414–3430 (1995)
Hussla, I. et al. Infrared-laser-induced photodesorption of NH3 and ND3 adsorbed on single-crystal Cu(100) and Ag film. Phys. Rev. B 32, 3489–3501 (1985)
Prybyla, J. A., Heinz, T. F., Misewich, J. A., Loy, M. M. T. & Glownia, J. H. Desorption induced by femtosecond laser pulses. Phys. Rev. Lett. 64, 1537–1540 (1990)
Salam, G. P., Persson, M. & Palmer, R. E. Possibility of coherent multiple excitation in atom transfer with a scanning tunneling microscope. Phys. Rev. B 49, 10655–10662 (1994)
Lorente, N. & Persson, M. Theory of single molecule vibrational spectroscopy and microscopy. Phys. Rev. Lett. 85, 2997–3000 (2000)
Lorente, N. & Persson, M. Theoretical aspects of tunneling-current-induced bond excitation and breaking at surfaces. Faraday Discuss. 117, 277–290 (2000)
J.I.P. acknowledges research contracts ‘Marie Curie’ (EU) and ‘Ramon y Cajal’ (Ministerio de Ciencia y Tecnología). N.L. acknowledges support from ACI Jeunes Chercheurs, and the CNRS programme ‘Nano-Objet Individuel’. All calculations were performed at the Centre d'Informatique National de l'Enseignement Supérieur (CINES) and the Centre de Calcul Midi-Pyrénées (CALMIP).
The authors declare that they have no competing financial interests.
About this article
Cite this article
Pascual, J., Lorente, N., Song, Z. et al. Selectivity in vibrationally mediated single-molecule chemistry. Nature 423, 525–528 (2003) doi:10.1038/nature01649
Electrical Engineering of the Oxygen Adatom and Vacancy on Rutile TiO2(110) by Atomic Force Microscopy at 78 K
The Journal of Physical Chemistry C (2019)
Quantum description of surface-enhanced resonant Raman scattering within a hybrid-optomechanical model
Physical Review A (2019)
Dissipation dynamics of intrachain exciton coupled with phonons in MEH‐PPV: Time‐resolved multiplex coherent anti‐Stokes Raman scattering
Journal of Raman Spectroscopy (2019)
Surface and Interface Analysis (2019)
Physical Review Letters (2019)