Chemical bond activation observed with an x-ray laser
Abstract
The concept of bonding and anti-bonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Lastly, we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding–anti-bonding splitting following bond-activation using an ultra short optical laser pulse.
- Authors:
-
more »
- Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); SLAC National Accelerator Lab., Menlo Park, CA (United States); Deutsches Elektronen-Synchrotron (DESY) Photon Science, Hamburg (Germany)
- Stockholm Univ., Stockholm, (Sweden)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Univ. Hamburg and Center for Free-Electron Laser Science, Hamburg (Germany)
- Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany)
- Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Chapman Univ., Orange, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Stockholm Univ., Stockholm, (Sweden)
- The Univ. of Liverpool, Liverpool (United Kingdom)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Stockholm Univ., Stockholm, (Sweden); KTH Royal Institute of Technology, Stockholm (Sweden)
- Fritz-Haber Institut der Max-Planck-Gesellschaft, Berlin (Germany)
- Deutsches Elektronen-Synchrotron (DESY) Photon Science, Hamburg (Germany); Univ. Hamburg and Center for Free-Electron Laser Science, Hamburg (Germany)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1349302
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 18; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Beye, Martin, Öberg, Henrik, Xin, Hongliang, Dakovski, Georgi L., Dell’Angela, Martina, Föhlisch, Alexander, Gladh, Jörgen, Hantschmann, Markus, Hieke, Florian, Kaya, Sarp, Kühn, Danilo, LaRue, Jerry, Mercurio, Giuseppe, Minitti, Michael P., Mitra, Ankush, Moeller, Stefan P., Ng, May Ling, Nilsson, Anders, Nordlund, Dennis, Nørskov, Jens, Öström, Henrik, Ogasawara, Hirohito, Persson, Mats, Schlotter, William F., Sellberg, Jonas A., Wolf, Martin, Abild-Pedersen, Frank, Pettersson, Lars G. M., and Wurth, Wilfried. Chemical bond activation observed with an x-ray laser. United States: N. p., 2016.
Web. doi:10.1021/acs.jpclett.6b01543.
Beye, Martin, Öberg, Henrik, Xin, Hongliang, Dakovski, Georgi L., Dell’Angela, Martina, Föhlisch, Alexander, Gladh, Jörgen, Hantschmann, Markus, Hieke, Florian, Kaya, Sarp, Kühn, Danilo, LaRue, Jerry, Mercurio, Giuseppe, Minitti, Michael P., Mitra, Ankush, Moeller, Stefan P., Ng, May Ling, Nilsson, Anders, Nordlund, Dennis, Nørskov, Jens, Öström, Henrik, Ogasawara, Hirohito, Persson, Mats, Schlotter, William F., Sellberg, Jonas A., Wolf, Martin, Abild-Pedersen, Frank, Pettersson, Lars G. M., & Wurth, Wilfried. Chemical bond activation observed with an x-ray laser. United States. https://doi.org/10.1021/acs.jpclett.6b01543
Beye, Martin, Öberg, Henrik, Xin, Hongliang, Dakovski, Georgi L., Dell’Angela, Martina, Föhlisch, Alexander, Gladh, Jörgen, Hantschmann, Markus, Hieke, Florian, Kaya, Sarp, Kühn, Danilo, LaRue, Jerry, Mercurio, Giuseppe, Minitti, Michael P., Mitra, Ankush, Moeller, Stefan P., Ng, May Ling, Nilsson, Anders, Nordlund, Dennis, Nørskov, Jens, Öström, Henrik, Ogasawara, Hirohito, Persson, Mats, Schlotter, William F., Sellberg, Jonas A., Wolf, Martin, Abild-Pedersen, Frank, Pettersson, Lars G. M., and Wurth, Wilfried. Thu .
"Chemical bond activation observed with an x-ray laser". United States. https://doi.org/10.1021/acs.jpclett.6b01543. https://www.osti.gov/servlets/purl/1349302.
@article{osti_1349302,
title = {Chemical bond activation observed with an x-ray laser},
author = {Beye, Martin and Öberg, Henrik and Xin, Hongliang and Dakovski, Georgi L. and Dell’Angela, Martina and Föhlisch, Alexander and Gladh, Jörgen and Hantschmann, Markus and Hieke, Florian and Kaya, Sarp and Kühn, Danilo and LaRue, Jerry and Mercurio, Giuseppe and Minitti, Michael P. and Mitra, Ankush and Moeller, Stefan P. and Ng, May Ling and Nilsson, Anders and Nordlund, Dennis and Nørskov, Jens and Öström, Henrik and Ogasawara, Hirohito and Persson, Mats and Schlotter, William F. and Sellberg, Jonas A. and Wolf, Martin and Abild-Pedersen, Frank and Pettersson, Lars G. M. and Wurth, Wilfried},
abstractNote = {The concept of bonding and anti-bonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Lastly, we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding–anti-bonding splitting following bond-activation using an ultra short optical laser pulse.},
doi = {10.1021/acs.jpclett.6b01543},
journal = {Journal of Physical Chemistry Letters},
number = 18,
volume = 7,
place = {United States},
year = {Thu Sep 01 00:00:00 EDT 2016},
month = {Thu Sep 01 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Cited by: 22 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Figure 1: (a): Top: The resonant absorption of an X-ray photon at the oxygen 1$s$ core level probes the unoccupied, antibonding states (green). Bottom: X-ray emission from the core-excited states represents the occupied $p$-density of states, mainly of bonding character.
All figures and tables
(4 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Why Must Oxygen Atoms Be Activated from Hollow Sites to Bridge Sites in Catalytic CO Oxidation?
journal, March 2000
- Zhang, C. J.; Hu, P.
- Journal of the American Chemical Society, Vol. 122, Issue 9
Phonon- Versus Electron-Mediated Desorption and Oxidation of CO on Ru(0001)
journal, August 1999
- Bonn, M.
- Science, Vol. 285, Issue 5430
Indication of non-thermal contribution to visible femtosecond laser-induced CO oxidation on Ru(0001)
journal, August 2015
- Öberg, H.; Gladh, J.; Marks, K.
- The Journal of Chemical Physics, Vol. 143, Issue 7
Chemical bonding on surfaces probed by X-ray emission spectroscopy and density functional theory
journal, October 2004
- Nilsson, Anders; Pettersson, Lars Gunnar Moody
- Surface Science Reports, Vol. 55, Issue 2-5
Real-Time Observation of Surface Bond Breaking with an X-ray Laser
journal, March 2013
- Dell'Angela, M.; Anniyev, T.; Beye, M.
- Science, Vol. 339, Issue 6125
Probing the transition state region in catalytic CO oxidation on Ru
journal, February 2015
- Öström, H.; Öberg, H.; Xin, H.
- Science, Vol. 347, Issue 6225
Ultrafast soft X-ray emission spectroscopy of surface adsorbates using an X-ray free electron laser
journal, April 2013
- Katayama, T.; Anniyev, T.; Beye, M.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 187
Time-resolved X-ray spectroscopies of chemical systems: New perspectives
journal, May 2016
- Chergui, Majed
- Structural Dynamics, Vol. 3, Issue 3
Local aspects of the adsorbate-substrate chemical bond in N/Cu(100) and O/Cu(100)
journal, July 1998
- Wiell, T.; Klepeis, J. E.; Bennich, P.
- Physical Review B, Vol. 58, Issue 3
Femtochemistry at Metal Surfaces: Nonadiabatic Reaction Dynamics
journal, October 2006
- Frischkorn, Christian; Wolf, Martin
- Chemical Reviews, Vol. 106, Issue 10
Ultra-fast dynamics of electron thermalization, cooling and transport effects in Ru(001)
journal, January 2004
- Lisowski, M.; Loukakos, P. A.; Bovensiepen, U.
- Applied Physics A: Materials Science & Processing, Vol. 78, Issue 2
The soft x-ray instrument for materials studies at the linac coherent light source x-ray free-electron laser
journal, April 2012
- Schlotter, W. F.; Turner, J. J.; Rowen, M.
- Review of Scientific Instruments, Vol. 83, Issue 4
Surface core-level shifts of clean and oxygen-covered Ru(0001)
journal, May 2001
- Lizzit, S.; Baraldi, A.; Groso, A.
- Physical Review B, Vol. 63, Issue 20
X-ray pulse preserving single-shot optical cross-correlation method for improved experimental temporal resolution
journal, March 2012
- Beye, M.; Krupin, O.; Hays, G.
- Applied Physics Letters, Vol. 100, Issue 12
Thermal evolution of the band edges of 6H-SiC: X-ray methods compared to the optical band gap
journal, December 2014
- Miedema, P. S.; Beye, M.; Könnecke, R.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 197
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Precursor-mediated adsorption and desorption: a theoretical analysis
journal, March 1988
- Doren, Douglas J.; Tully, John C.
- Langmuir, Vol. 4, Issue 2
Dynamics of precursor‐mediated chemisorption
journal, June 1991
- Doren, Douglas J.; Tully, John C.
- The Journal of Chemical Physics, Vol. 94, Issue 12
Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method
journal, June 2010
- Enkovaara, J.; Rostgaard, C.; Mortensen, J. J.
- Journal of Physics: Condensed Matter, Vol. 22, Issue 25
Calculations of X-ray Emission Spectra of Molecules and Surface Adsorbates by Means of Density Functional Theory
journal, December 1998
- Triguero, L.; Pettersson, L. G. M.; Ågren, H.
- The Journal of Physical Chemistry A, Vol. 102, Issue 52
An implementation of core level spectroscopies in a real space Projector Augmented Wave density functional theory code
journal, November 2011
- Ljungberg, M. P.; Mortensen, J. J.; Pettersson, L. G. M.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 8-10
Works referencing / citing this record:
Short-wavelength free-electron laser sources and science: a review
text, January 2017
- Seddon, E. A.; Clarke, J. A.; Dunning, D. J.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
In Situ/Operando Characterization Techniques to Probe the Electrochemical Reactions for Energy Conversion
journal, April 2018
- Li, Xuning; Wang, Hsin-Yi; Yang, Hongbin
- Small Methods, Vol. 2, Issue 6
Quantum-Sized Metal Catalysts for Hot-Electron-Driven Chemical Transformation
journal, August 2018
- Wei, Qilin; Wu, Siyu; Sun, Yugang
- Advanced Materials, Vol. 30, Issue 48
Theoretical X‐ray spectroscopy of transition metal compounds
journal, July 2019
- Bokarev, Sergey I.; Kühn, Oliver
- WIREs Computational Molecular Science, Vol. 10, Issue 1
Atom-specific activation in CO oxidation
journal, December 2018
- Schreck, Simon; Diesen, Elias; LaRue, Jerry
- The Journal of Chemical Physics, Vol. 149, Issue 23
Atom-specific activation in CO oxidation
text, January 2018
- Schreck, Simon; Diesen, Elias; LaRue, Jerry
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Short-wavelength free-electron laser sources and science: a review
journal, October 2017
- Seddon, E. A.; Clarke, J. A.; Dunning, D. J.
- Reports on Progress in Physics, Vol. 80, Issue 11
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.