- Physical Review Journals
All JournalsPhysics Magazine

Physical Review X

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 3.0 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
  • Open Access

Electronic Predetermination of Ethylene Fragmentation Dynamics

Xinhua Xie1,*, Stefan Roither1, Markus Schöffler1, Erik Lötstedt2,‡, Daniil Kartashov1, Li Zhang1, Gerhard G. Paulus3,4, Atsushi Iwasaki2, Andrius Baltuška1 et al.

Kaoru Yamanouchi2 and Markus Kitzler1,†

  • 1Photonics Institute, Vienna University of Technology, Gusshausstrasse 27, A-1040 Vienna, Austria, EU
  • 2Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
  • 3Institute of Optics and Quantum Electronics, Friedrich-Schiller-University Jena, D-07743 Jena, Germany, EU
  • 4Helmholtz Institute Jena, D-07743 Jena, Germany, EU

  • *xinhua.xie@tuwien.ac.at
  • †markus.kitzler@tuwien.ac.at
  • ‡Present address: Laser Technology Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
PDF

Phys. Rev. X 4, 021005 – Published 7 April, 2014

DOI: https://doi.org/10.1103/PhysRevX.4.021005

Abstract

We experimentally investigate the dependence of the fragmentation behavior of the ethylene dication on the intensity and duration of the laser pulses that initiate the fragmentation dynamics by strong-field double ionization. Using coincidence momentum imaging for the detection of ionic fragments, we disentangle the different contributions of ionization from lower-valence orbitals and field-driven excitation dynamics to the population of certain dissociative excited ionic states that are connected to one of several possible fragmentation pathways towards a given set of fragment ions. We find that the excitation probability to a particular excited state and therewith the outcome of the fragmentation reaction strongly depend on the parameters of the laser pulse. This, in turn, opens up new possibilities for controlling the outcome of fragmentation reactions of polyatomic molecules in that it may allow one to selectively enhance or suppress individual fragmentation channels, which was not possible in previous attempts of controlling fragmentation processes of polyatomic molecules with strong laser fields.

View figure in article

Viewpoint

Controlling a Molecule’s Fate

Published 7 April, 2014

By selecting the intensity and duration of an ultrashort laser pulse, researchers are able to control the breakup of a molecule through the relation between its electrons and nuclei.

See more in Physics

Popular Summary

In molecules, the constituent atoms are bound together by their electrons, whose motions can be very fast. Rearranging the atoms, or splitting them apart, is ultimately determined by the electrons. A fundamentally important and fascinating question is then to what extent, and by which mechanisms, electronic processes can influence the slower molecular restructuring and splitting processes, or even determine their outcome. The answer to this question may also guide the design of novel methods for controlling chemical reactions. In this experimental paper, we demonstrate that selective fragmentation of ethylene molecules can be achieved by controlled distortion of the electron cloud induced by quickly ripping off two electrons with strong and very short laser pulses.

Depending on the quantum states (molecular orbitals) the electrons are removed from, the ionization of the molecule triggers the motion of the heavy atoms and may eventually lead to a split of the molecule into two ionic fragments. But, knowing what the two fragments are does not immediately tell us which molecular orbitals the electrons are removed from, as different pathways can lead to the same ionic fragments. By analyzing the energies and directions of the two fragments against possible fragmentation pathways and quantum-chemical simulations, we have identified, for a number of fragmentation pathways, their corresponding molecular orbitals. Furthermore, our results show that the parameters of the laser pulses, specifically intensity and duration, can be used to select the fragmentation pathway.

Our work may open up new possibilities for controlling the outcome of fragmentation reactions of polyatomic molecules such as the selective enhancement or suppression of specific combinations of fragments.

Article Text

References (56)

  1. H. Xu, T. Okino, K. Nakai, K. Yamanouchi, S. Roither, X. Xie, D. Kartashov, M. Schöffler, A. Baltuska, and M. Kitzler, Hydrogen Migration and C−C Bond Breaking in 1,3-Butadiene in Intense Laser Fields Studied by Coincidence Momentum Imaging, Chem. Phys. Lett. 484, 119 (2010).
  2. M. F. Kling, P. von den Hoff, I. Znakovskaya, and R. de Vivie-Riedle, (Sub-)Femtosecond Control of Molecular Reactions via Tailoring the Electric Field of Light, Phys. Chem. Chem. Phys. 15, 9448 (2013).
  3. M. Kremer, B. Fischer, B. Feuerstein, V. L. B. de Jesus, V. Sharma, C. Hofrichter, A. Rudenko, U. Thumm, C. D. Schröter, R. Moshammer, and J. Ullrich, Electron Localization in Molecular Fragmentation of H2 by Carrier-Envelope Phase Stabilized Laser Pulses, Phys. Rev. Lett. 103, 213003 (2009).
  4. Y. Liu, X. Liu, Y. Deng, C. Wu, H. Jiang, and Q. Gong, Selective Steering of Molecular Multiple Dissociative Channels with Strong Few-Cycle Laser Pulses, Phys. Rev. Lett. 106, 073004 (2011).
  5. T. Rathje, A. M. Sayler, S. Zeng, P. Wustelt, H. Figger, B. D. Esry, and G. G. Paulus, Coherent Control at Its Most Fundamental: Carrier-Envelope-Phase-Dependent Electron Localization in Photodissociation of a H2+ Molecular Ion Beam Target, Phys. Rev. Lett. 111, 093002 (2013).
  6. X. Xie, K. Doblhoff-Dier, S. Roither, M. S. Schöffler, D. Kartashov, H. Xu, T. Rathje, G. G. Paulus, A. Baltuška, S. Gräfe, and M. Kitzler, Attosecond-Recollision-Controlled Selective Fragmentation of Polyatomic Molecules, Phys. Rev. Lett. 109, 243001 (2012).
  7. A. E. Boguslavskiy, J. Mikosch, A. Gijsbertsen, M. Spanner, S. Patchkovskii, N. Gador, M. J. J. Vrakking, and A. Stolow The Multielectron Ionization Dynamics Underlying Attosecond Strong-Field Spectroscopies, Science 335, 1336 (2012).
  8. K. Hosaka, A. Yokoyama, K. Yamanouchi, and R. Itakura, Correlation Between a Photoelectron and a Fragment Ion in Dissociative Ionization of Ethanol in Intense Near-Infrared Laser Fields, J. Chem. Phys. 138, 204301 (2013).
  9. M. Lezius, V. Blanchet, M. Y. Ivanov, and A. Stolow, Polyatomic Molecules in Strong Laser Fields: Nonadiabatic Multielectron Dynamics, J. Chem. Phys. 117, 1575 (2002).
  10. A. N. Markevitch, S. M. Smith, D. A. Romanov, H. B. Schlegel, M. Y. Ivanov, and R. J. Levis, Nonadiabatic Dynamics of Polyatomic Molecules and Ions in Strong Laser Fields, Phys. Rev. A 68, 011402(R) (2003).
  11. I. Znakovskaya, P. von den Hoff, S. Zherebtsov, A. Wirth, O. Herrwerth, M. J. J. Vrakking, R. de Vivie-Riedle, and M. F. Kling, Attosecond Control of Electron Dynamics in Carbon Monoxide, Phys. Rev. Lett. 103, 103002 (2009).
  12. Y. Mairesse, J. Higuet, N. Dudovich, D. Shafir, B. Fabre, E. Mével, E. Constant, S. Patchkovskii, Z. Walters, M. Y. Ivanov, and O. Smirnova, High Harmonic Spectroscopy of Multichannel Dynamics in Strong-Field Ionization, Phys. Rev. Lett. 104, 213601 (2010).
  13. H. W. van der Hart, Sequential Versus Non-Sequential Double Ionization in Strong Laser Fields, J. Phys. B 33, L699 (2000).
  14. V. L. B. de Jesus, B. Feuerstein, K. Zrost, D. Fischer, A. Rudenko, F. Afaneh, C. D. Schröter, R. Moshammer, and J. Ullrich, Atomic Structure Dependence of Nonsequential Double Ionization of He, Ne and Ar in Strong Laser Pulses, J. Phys. B 37, L161 (2004).
  15. A. Rudenko, K. Zrost, B. Feuerstein, V. L. B. de Jesus, C. D. Schröter, R. Moshammer, and J. Ullrich, Correlated Multielectron Dynamics in Ultrafast Laser Pulse Interactions with Atoms, Phys. Rev. Lett. 93, 253001 (2004).
  16. L. Zhang, S. Roither, X. Xie, D. Kartashov, M. Schöffler, H. Xu, A. Iwasaki, S. Gräfe, T. Okino, K. Yamanouchi, A. Baltuska, and M. Kitzler, Path-Selective Investigation of Intense Laser-Pulse-Induced Fragmentation Dynamics in Triply Charged 1,3-Butadiene, J. Phys. B 45, 085603 (2012).
  17. H. Xu, T. Okino, T. Kudou, K. Yamanouchi, S. Roither, M. Kitzler, A. Baltuska, and S.-L. Chin, Effect of Laser Parameters on Ultrafast Hydrogen Migration in Methanol Studied by Coincidence Momentum Imaging, J. Phys. Chem. A 116, 2686 (2012).
  18. S. M. Sharifi, A. Talebpour, and S. L. Chin, Double Ionization of Benzene Interacting with Strong Ti:Sapphire Laser Pulses, J. Phys. B 40, F259 (2007).
  19. S. M. Sharifi, A. Talebpour, and S. L. Chin, Double Ionization of Unsaturated Hydrocarbons Interacting with High-Power Femtosecond Laser Pulses, J. At. Mol. Opt. Phys. 2009, 1 (2009).
  20. C. Cornaggia and P. Hering, Nonsequential Double Ionization of Small Molecules Induced by a Femtosecond Laser Field, Phys. Rev. A 62, 023403 (2000).
  21. A. Hishikawa, H. Hasegawa, and K. Yamanouchi, Hydrogen Migration in Acetonitrile in Intense Laser Fields in Competition with Two-Body Coulomb Explosion, J. Electron Spectrosc. Relat. Phenom. 141, 195 (2004).
  22. M. Pitzer, M. Kunitski, A. S. Johnson, T. Jahnke, H. Sann, F. Sturm, L. P. H. Schmidt, H. Schmidt-Böcking, R. Dörner, J. Stohner, J. Kiedrowski, M. Reggelin, S. Marquardt, A. Schießer, R. Berger, and M. S. Schöffler, Direct Determination of Absolute Molecular Stereochemistry in Gas Phase by Coulomb Explosion Imaging, Science 341, 1096 (2013).
  23. A. Hishikawa, A. Matsuda, M. Fushitani, and E. J. Takahashi, Visualizing Recurrently Migrating Hydrogen in Acetylene Dication by Intense Ultrashort Laser Pulses, Phys. Rev. Lett. 99, 258302 (2007).
  24. T. Ikuta, K. Hosaka, H. Akagi, A. Yokoyama, K. Yamanouchi, F. Kannari, and R. Itakura, Separation of Ionization and Subsequent Electronic Excitation for Formation of Electronically Excited Ethanol Cation in Intense Laser Fields, J. Phys. B 44, 191002 (2011).
  25. S. Roither, X. Xie, D. Kartashov, L. Zhang, M. Schöffler, H. Xu, A. Iwasaki, T. Okino, K. Yamanouchi, A. Baltuska, and M. Kitzler, High Energy Proton Ejection from Hydrocarbon Molecules Driven by Highly Efficient Field Ionization, Phys. Rev. Lett. 106, 163001 (2011).
  26. C. Cornaggia, M. Schmidt, and D. Normand, Laser-Induced Nuclear Motions in the Coulomb Explosion of C2H2+ Ions, Phys. Rev. A 51, 1431 (1995).
  27. S. Palaniyappan, R. Mitchell, N. Ekanayake, A. M. Watts, S. L. White, R. Sauer, L. E. Howard, M. Videtto, C. Mancuso, S. J. Wells, T. Stanev, B. L. Wen, M. F. Decamp, and B. C. Walker, Ionization of Ethane, Butane, and Octane in Strong Laser Fields, Phys. Rev. A 82, 043433 (2010).
  28. R. Dörner, V. Mergel, O. Jagutzki, L. Spielberger, J. Ullrich, R. Moshammer, and H. Schmidt-Böcking, Cold Target Recoil Ion Momentum Spectroscopy: A ‘Momentum Microscope’ to View Atomic Collision Dynamics, Phys. Rep. 330, 95 (2000).
  29. J. Ullrich, R. Moshammer, A. Dorn, R. Dörner, L. P. H. Schmidt, and H. Schmidt-Böcking, Recoil-Ion and Electron Momentum Spectroscopy: Reaction-Microscopes, Rep. Prog. Phys. 66, 1463 (2003).
  30. X. Xie, S. Roither, D. Kartashov, E. Persson, D. G. Arbó, L. Zhang, S. Gräfe, M. S. Schöffler, J. Burgdörfer, A. Baltuška, and M. Kitzler, Attosecond Probe of Valence-Electron Wave Packets by Subcycle Sculpted Laser Fields, Phys. Rev. Lett. 108, 193004 (2012).
  31. A. M. Sayler, T. Rathje, W. Müller, C. Kürbis, K. Rühle, G. Stibenz, and G. G. Paulus, Real-Time Pulse Length Measurement of Few-Cycle Laser Pulses Using Above-Threshold Ionization, Opt. Express 19, 4464 (2011).
  32. A. M. Sayler, T. Rathje, W. Müller, K. Rühle, R. Kienberger, and G. G. Paulus, Precise, Real-Time, Every-Single-Shot, Carrier-Envelope Phase Measurement of Ultrashort Laser Pulses, Opt. Lett. 36, 1 (2011).
  33. A. S. Alnaser, X. M. Tong, T. Osipov, S. Voss, C. M. Maharjan, B. Shan, Z. Chang, and C. L. Cocke, Laser-Peak-Intensity Calibration Using Recoil-Ion Momentum Imaging, Phys. Rev. A 70, 023413 (2004).
  34. A. D. Yau, S. A. Perera, and R. J. Bartlett, Vertical Ionization Potentials of Ethylene: The Right Answer for the Right Reason?, Mol. Phys. 100, 835 (2002).
  35. E. Ohrendorf, H. Köppel, L. S. Cederbaum, F. Tarantelli, and A. Sgamellotti, Doubly Ionized States of Ethylene: Auger Spectrum, Potential Energy Surfaces and Nuclear Dynamics, J. Chem. Phys. 91, 1734 (1989).
  36. L. V. Keldysh, Ionization in the Field of a Strong Electromagnetic Wave, Zh. Eksp. Teor. Fiz. 47, 1945 (1964) [Sov. Phys. JETP 20, 1307 (1965)].
  37. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery, Jr., General Atomic and Molecular Electronic Structure System, J. Comput. Chem. 14, 1347 (1993).
  38. C.-M. Liegener, Calculations on the Auger Spectra of Ethylene and Acetylene, Chem. Phys. 92, 97 (1985).
  39. T. Ibuki, T. Imamura, I. Koyano, T. Masuoka, and C. E. Brion, Dissociation of Doubly Charged CH2=CD2 and CH2=CF2 in the Region of Valence Shell Photoexcitation, J. Chem. Phys. 98, 2908 (1993).
  40. B. K. McFarland, J. P. Farrell, P. H. Bucksbaum, and M. Gühr, High Harmonic Generation from Multiple Orbitals in N2, Science 322, 1232 (2008).
  41. P. von den Hoff, I. Znakovskaya, S. Zherebtsov, M. F. Kling, and R. de Vivie-Riedle, Effects of Multi Orbital Contributions in the Angular-Dependent Ionization of Molecules in Intense Few-Cycle Laser Pulses, Appl. Phys. B 98, 659 (2010).
  42. H. Akagi, T. Otobe, A. Staudte, A. Shiner, F. Turner, R. Dörner, D. M. Villeneuve, and P. B. Corkum, Laser Tunnel Ionization from Multiple Orbitals in HCl, Science 325, 1364 (2009).
  43. C. Wu, H. Zhang, H. Yang, Q. Gong, D. Song, and H. Su, Tunneling Ionization of Carbon Dioxide from Lower-Lying Orbitals, Phys. Rev. A 83, 033410 (2011).
  44. J. P. Farrell, S. Petretti, J. Förster, B. K. McFarland, L. S. Spector, Y. V. Vanne, P. Decleva, P. H. Bucksbaum, A. Saenz, and M. Gühr, Strong Field Ionization to Multiple Electronic States in Water, Phys. Rev. Lett. 107, 083001 (2011).
  45. X. M. Tong, Z. X. Zhao, and C. D. Lin, Theory of Molecular Tunneling Ionization, Phys. Rev. A 66, 033402 (2002).
  46. D. Pavičić, K. F. Lee, D. M. Rayner, P. B. Corkum, and D. M. Villeneuve, Direct Measurement of the Angular Dependence of Ionization for N2, O2, and CO2 in Intense Laser Fields, Phys. Rev. Lett. 98, 243001 (2007).
  47. K. Lammertsma, M. Barzaghi, G. A. Olah, J. A. Pople, A. J. Kos, and P. v. R. Schleyer, The Ethylene Dication: A Theoretical Study of The Ethylene Dication (C2H42+) Potential-Energy Surface, J. Am. Chem. Soc. 105, 5252 (1983).
  48. X. M. Tong, Z. X. Zhao, A. S. Alnaser, S. Voss, C. L. Cocke, and C. D. Lin, Post Ionization Alignment of the Fragmentation of Molecules in an Ultrashort Intense Laser Field, J. Phys. B 38, 333 (2005).
  49. T. Zuo and A. D. Bandrauk, Charge-Resonance-Enhanced Ionization of Diatomic Molecular Ions by Intense Lasers, Phys. Rev. A 52, R2511 (1995).
  50. E. Lötstedt, T. Kato, and K. Yamanouchi, Enhanced Ionization of Acetylene in Intense Laser Fields, Phys. Rev. A 85, 041402 (2012).
  51. S. Bubin, M. Atkinson, K. Varga, X. Xie, S. Roither, D. Kartashov, A. Baltuška, and M. Kitzler, Strong Laser-Pulse-Driven Ionization and Coulomb Explosion of Hydrocarbon Molecules, Phys. Rev. A 86, 043407 (2012).
  52. X. Xie, S. Roither, M. Schöffler, S. Bubin, H. Xu, S. Erattuphuza, A. Iwasaki, K. Varga, D. Kartashov, G. Paulus, K. Yamanouchi, A. Baltuska, and M. Kitzler, Role of Proton Dynamics in Efficient Photoionization of Hydrocarbon Molecules, Phys. Rev. A 89, 023429 (2014).
  53. R. Torres, N. Kajumba, J. G. Underwood, J. S. Robinson, S. Baker, J. W. G. Tisch, R. de Nalda, W. A. Bryan, R. Velotta, C. Altucci, I. C. E. Turcu, and J. P. Marangos, Probing Orbital Structure of Polyatomic Molecules by High-Order Harmonic Generation, Phys. Rev. Lett. 98, 203007 (2007).
  54. C. I. Blaga, J. Xu, A. D. DiChiara, E. Sistrunk, K. Zhang, P. Agostini, T. A. Miller, L. F. DiMauro, and C. D. Lin, Imaging Ultrafast Molecular Dynamics with Laser-Induced Electron Diffraction, Nature (London) 483, 194 (2012).
  55. L. Holmegaard, J. L. Hansen, L. Kalhøj, S. Louise Kragh, H. Stapelfeldt, F. Filsinger, J. Küpper, G. Meijer, D. Dimitrovski, M. Abu-samha, C. P. J. Martiny, and L. Bojer Madsen, Photoelectron Angular Distributions from Strong-Field Ionization of Oriented Molecules, Nat. Phys. 6, 428 (2010).
  56. J. L. Hansen, L. Holmegaard, J. H. Nielsen, H. Stapelfeldt, D. Dimitrovski, and L. B. Madsen, Orientation-Dependent Ionization Yields from Strong-Field Ionization of Fixed-in-Space Linear and Asymmetric Top Molecules, J. Phys. B 45, 015101 (2012).

Outline

Information

Phys. Rev. X 4, 021005– Published 7 April, 2014
  • Received 14 October 2013
Creative Commons Logo

This article is available under the terms of the Creative Commons Attribution 3.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation