TY  - JOUR
A1  - Dell'Angela, M.
A1  - Anniyev, Toyli
A1  - Beye, Martin
A1  - Coffee, Ryan
A1  - Föhlisch, Alexander
A1  - Gladh, J.
A1  - Katayama, T.
A1  - Kaya, S.
A1  - Krupin, O.
A1  - LaRue, J.
A1  - Mogelhoj, A.
A1  - Nordlund, D.
A1  - Norskov, J. K.
A1  - Oberg, H.
A1  - Ogasawara, H.
A1  - Ostrom, H.
A1  - Pettersson, Lars G. M.
A1  - Schlotter, W. F.
A1  - Sellberg, J. A.
A1  - Sorgenfrei, Florian
A1  - Turner, J. J.
A1  - Wolf, M.
A1  - Wurth, W.
A1  - Nilsson, A.
T1  - Real-time observation of surface bond breaking with an X-ray Laser
JF  - Science
N2  - We used the Linac Coherent Light Source free-electron x-ray laser to probe the electronic structure of CO molecules as their chemisorption state on Ru(0001) changes upon exciting the substrate by using a femtosecond optical laser pulse. We observed electronic structure changes that are consistent with a weakening of the CO interaction with the substrate but without notable desorption. A large fraction of the molecules (30%) was trapped in a transient precursor state that would precede desorption. We calculated the free energy of the molecule as a function of the desorption reaction coordinate using density functional theory, including van der Waals interactions. Two distinct adsorption wells-chemisorbed and precursor state separated by an entropy barrier-explain the anomalously high prefactors often observed in desorption of molecules from metals.
Y1  - 2013
U6  - https://doi.org/10.1126/science.1231711
SN  - 0036-8075
VL  - 339
IS  - 6125
SP  - 1302
EP  - 1305
PB  - American Assoc. for the Advancement of Science
CY  - Washington
ER  - 
TY  - JOUR
A1  - Beye, Martin
A1  - Anniyev, Toyli
A1  - Coffee, Ryan
A1  - Dell'Angela, Martina
A1  - Föhlisch, Alexander
A1  - Gladh, J.
A1  - Katayama, T.
A1  - Kaya, S.
A1  - Krupin, O.
A1  - Mogelhoj, A.
A1  - Nilsson, A.
A1  - Nordlund, D.
A1  - Norskov, J. K.
A1  - Oberg, H.
A1  - Ogasawara, H.
A1  - Pettersson, Lars G. M.
A1  - Schlotter, W. F.
A1  - Sellberg, J. A.
A1  - Sorgenfrei, Florian
A1  - Turner, J. J.
A1  - Wolf, M.
A1  - Wurth, Wilfried
A1  - Ostrom, H.
T1  - Selective ultrafast probing of transient hot chemisorbed and precursor States of CO on Ru(0001)
JF  - Physical review letters
N2  - We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.
Y1  - 2013
U6  - https://doi.org/10.1103/PhysRevLett.110.186101
SN  - 0031-9007
VL  - 110
IS  - 18
PB  - American Physical Society
CY  - College Park
ER  - 
TY  - JOUR
A1  - Ostrom, H.
A1  - Oberg, H.
A1  - Xin, H.
A1  - Larue, J.
A1  - Beye, Martin
A1  - Gladh, J.
A1  - Ng, M. L.
A1  - Sellberg, J. A.
A1  - Kaya, S.
A1  - Mercurio, G.
A1  - Nordlund, D.
A1  - Hantschmann, Markus
A1  - Hieke, F.
A1  - Kuehn, D.
A1  - Schlotter, W. F.
A1  - Dakovski, G. L.
A1  - Turner, J. J.
A1  - Minitti, M. P.
A1  - Mitra, A.
A1  - Moeller, S. P.
A1  - Föhlisch, Alexander
A1  - Wolf, M.
A1  - Wurth, W.
A1  - Persson, Mats
A1  - Norskov, J. K.
A1  - Abild-Pedersen, Frank
A1  - Ogasawara, Hirohito
A1  - Pettersson, Lars G. M.
A1  - Nilsson, A.
T1  - Probing the transition state region in catalytic CO oxidation on Ru
JF  - Science
N2  - Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the OK-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.
Y1  - 2015
U6  - https://doi.org/10.1126/science.1261747
SN  - 0036-8075
SN  - 1095-9203
VL  - 347
IS  - 6225
SP  - 978
EP  - 982
PB  - American Assoc. for the Advancement of Science
CY  - Washington
ER  - 
TY  - JOUR
A1  - Katayama, T.
A1  - Anniyev, Toyli
A1  - Beye, Martin
A1  - Coffee, Ryan
A1  - Dell'Angela, M.
A1  - Föhlisch, Alexander
A1  - Gladh, J.
A1  - Kaya, S.
A1  - Krupin, O.
A1  - Nilsson, A.
A1  - Nordlund, D.
A1  - Schlotter, W. F.
A1  - Sellberg, J. A.
A1  - Sorgenfrei, Florian
A1  - Turner, J. J.
A1  - Wurth, W.
A1  - Öström, H.
A1  - Ogasawara, H.
T1  - Ultrafast soft X-ray emission spectroscopy of surface adsorbates using an X-ray free electron laser
JF  - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy
N2  - We report on an experimental system designed to probe chemical reactions on solid surfaces on a sub-picosecond timescale using soft X-ray emission spectroscopy at the Linac Coherent Light Source (LCLS) free electron laser (FEL) at the SLAC National Accelerator Laboratory. We analyzed the O 1s X-ray emission spectra recorded from atomic oxygen adsorbed on a Ru(0001) surface at a synchrotron beamline (SSRL, BL13-2) and an FEL beamline (LCLS, SXR). We have demonstrated conditions that provide negligible amount of FEL induced damage of the sample. In addition we show that the setup is capable of tracking the temporal evolution of electronic structure during a surface reaction of submonolayer quantities of CO molecules desorbing from the surface.
KW  - X-ray emission spectroscopy
KW  - Surface science
KW  - Free electron laser
KW  - Ultrafast
Y1  - 2013
U6  - https://doi.org/10.1016/j.elspec.2013.03.006
SN  - 0368-2048
VL  - 187
IS  - 1
SP  - 9
EP  - 14
PB  - Elsevier
CY  - Amsterdam
ER  - 
TY  - JOUR
A1  - Oberg, H.
A1  - Gladh, Jörgen
A1  - Anniyev, Toyli
A1  - Beye, Martin
A1  - Coffee, Ryan
A1  - Föhlisch, Alexander
A1  - Katayama, T.
A1  - Kaya, Sarp
A1  - LaRue, Jerry
A1  - Mogelhoj, Andreas
A1  - Nordlund, Dennis
A1  - Ogasawara, Hirohito
A1  - Schlotter, William F.
A1  - Sellberg, Jonas A.
A1  - Sorgenfrei, Florian
A1  - Turner, Joshua J.
A1  - Wolf, Martin
A1  - Wurth, W.
A1  - Ostrom, Henrik
A1  - Nilsson, Anders
A1  - Norskov, Jens K.
A1  - Pettersson, Lars G. M.
T1  - Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state
JF  - Surface science
N2  - We present density functional theory modeling of time-resolved optical pump/X-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as a precursor to desorption. The optical pump leads to a near-instantaneous (<100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of similar to 2000K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor states, and becomes significant at the elevated temperature of the experiment (similar to 1.4 eV at 2000 K). Experimental pump-probe X-ray absorption/X-ray emission spectroscopy indicates population of a precursor state to desorption upon laser-excitation of the system (Dell'Angela et al., 2013). Computing spectra along the desorption path confirms the picture of a weakly bound transient state arising from ultrafast heating of the metal substrate. (C) 2015 Elsevier B.V. All rights reserved.
KW  - CO desorption
KW  - Potential of mean force
KW  - Two-temperature model
KW  - Pump-probe
KW  - X-ray spectroscopy
KW  - Density functional theory
Y1  - 2015
U6  - https://doi.org/10.1016/j.susc.2015.03.011
SN  - 0039-6028
SN  - 1879-2758
VL  - 640
SP  - 80
EP  - 88
PB  - Elsevier
CY  - Amsterdam
ER  -