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Title: Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy

Abstract

The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds. Most of the CO molecules trapped in the precursor state ultimately cooled back down to the chemisorbed state, while we estimate that ~14.5 ± 4.9% of the molecules in the precursor state desorbed into the gas phase. Finally, it was also observed that chemisorbed CO molecules diffused over the metal surface from on-top sites toward highly coordinated sites. In addition, a new “vibrationally hot precursor” state was identified in the polarization-dependent XA spectra.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [1]; ORCiD logo [4];  [5];  [5];  [5];  [5];  [5];  [5];  [5];  [6];  [1];  [1]; ORCiD logo [1];  [1] more »;  [6]; ORCiD logo [7];  [1]; ORCiD logo [1] « less
  1. Stockholm Univ. (Sweden)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Chapman Univ., Orange, CA (United States)
  4. CNR-IOM, Trieste (Italy)
  5. FERMI, Trieste (Italy)
  6. German Electron Synchrotron (DESY) Photon Science, Hamburg (Germany)
  7. CNR-IOM, Trieste (Italy); Univ. of Trieste (Italy)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Knut and Alice Wallenberg Foundation; Swedish Research Council (SRC); Helmholtz Association
OSTI Identifier:
1608907
Alternate Identifier(s):
OSTI ID: 1562549
Grant/Contract Number:  
KAW 2014.0370; VH-NG-1005; RBSI14G7TL; CUP B82I15000910001; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 22; Journal Issue: 5; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Hsin-Yi, Schreck, Simon, Weston, Matthew, Liu, Chang, Ogasawara, Hirohito, LaRue, Jerry, Perakis, Fivos, Dell’Angela, Martina, Capotondi, Flavio, Giannessi, Luca, Pedersoli, Emanuele, Naumenko, Denys, Nikolov, Ivaylo, Raimondi, Lorenzo, Spezzani, Carlo, Beye, Martin, Cavalca, Filippo, Liu, Boyang, Gladh, Jörgen, Koroidov, Sergey, Miedema, Piter S., Costantini, Roberto, Pettersson, Lars G. M., and Nilsson, Anders. Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy. United States: N. p., 2019. Web. https://doi.org/10.1039/c9cp03677f.
Wang, Hsin-Yi, Schreck, Simon, Weston, Matthew, Liu, Chang, Ogasawara, Hirohito, LaRue, Jerry, Perakis, Fivos, Dell’Angela, Martina, Capotondi, Flavio, Giannessi, Luca, Pedersoli, Emanuele, Naumenko, Denys, Nikolov, Ivaylo, Raimondi, Lorenzo, Spezzani, Carlo, Beye, Martin, Cavalca, Filippo, Liu, Boyang, Gladh, Jörgen, Koroidov, Sergey, Miedema, Piter S., Costantini, Roberto, Pettersson, Lars G. M., & Nilsson, Anders. Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy. United States. https://doi.org/10.1039/c9cp03677f
Wang, Hsin-Yi, Schreck, Simon, Weston, Matthew, Liu, Chang, Ogasawara, Hirohito, LaRue, Jerry, Perakis, Fivos, Dell’Angela, Martina, Capotondi, Flavio, Giannessi, Luca, Pedersoli, Emanuele, Naumenko, Denys, Nikolov, Ivaylo, Raimondi, Lorenzo, Spezzani, Carlo, Beye, Martin, Cavalca, Filippo, Liu, Boyang, Gladh, Jörgen, Koroidov, Sergey, Miedema, Piter S., Costantini, Roberto, Pettersson, Lars G. M., and Nilsson, Anders. Mon . "Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy". United States. https://doi.org/10.1039/c9cp03677f. https://www.osti.gov/servlets/purl/1608907.
@article{osti_1608907,
title = {Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy},
author = {Wang, Hsin-Yi and Schreck, Simon and Weston, Matthew and Liu, Chang and Ogasawara, Hirohito and LaRue, Jerry and Perakis, Fivos and Dell’Angela, Martina and Capotondi, Flavio and Giannessi, Luca and Pedersoli, Emanuele and Naumenko, Denys and Nikolov, Ivaylo and Raimondi, Lorenzo and Spezzani, Carlo and Beye, Martin and Cavalca, Filippo and Liu, Boyang and Gladh, Jörgen and Koroidov, Sergey and Miedema, Piter S. and Costantini, Roberto and Pettersson, Lars G. M. and Nilsson, Anders},
abstractNote = {The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds. Most of the CO molecules trapped in the precursor state ultimately cooled back down to the chemisorbed state, while we estimate that ~14.5 ± 4.9% of the molecules in the precursor state desorbed into the gas phase. Finally, it was also observed that chemisorbed CO molecules diffused over the metal surface from on-top sites toward highly coordinated sites. In addition, a new “vibrationally hot precursor” state was identified in the polarization-dependent XA spectra.},
doi = {10.1039/c9cp03677f},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 5,
volume = 22,
place = {United States},
year = {2019},
month = {9}
}

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