Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast X-ray spectroscopy and ab initio simulations

H. Xin; J. Larue; H. Öberg; M. Beye; M. Dell'Angela; J. J. Turner; J. Gladh; M. L. Ng; J. A. Sellberg; S. Kaya; G. Mercurio; F. Hieke; D. Nordlund; W. F. Schlotter; G. L. Dakovski; M. P. Minitti; A. Föhlisch; M. Wolf; W. Wurth; H. Ogasawara; J. K. Nørskov; H. Öström; L. G.M. Pettersson; A. Nilsson; F. Abild-Pedersen

doi:10.1103/PhysRevLett.114.156101

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast X-ray spectroscopy and ab initio simulations

H. Xin, J. Larue, H. Öberg, M. Beye, M. Dell'Angela, J. J. Turner, J. Gladh, M. L. Ng, J. A. Sellberg, S. Kaya, G. Mercurio, F. Hieke, D. Nordlund, W. F. Schlotter, G. L. Dakovski, M. P. Minitti, A. Föhlisch, M. Wolf, W. Wurth, H. OgasawaraJ. K. Nørskov, H. Öström, L. G.M. Pettersson, A. Nilsson, F. Abild-Pedersen

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Abstract

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.

Original language	English
Article number	156101
Journal	Physical Review Letters
Volume	114
Issue number	15
Number of pages	6
ISSN	0031-9007
DOIs	https://doi.org/10.1103/PhysRevLett.114.156101
Publication status	Published - 2015
Externally published	Yes

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Xin, H., Larue, J., Öberg, H., Beye, M., Dell'Angela, M., Turner, J. J., Gladh, J., Ng, M. L., Sellberg, J. A., Kaya, S., Mercurio, G., Hieke, F., Nordlund, D., Schlotter, W. F., Dakovski, G. L., Minitti, M. P., Föhlisch, A., Wolf, M., Wurth, W., ... Abild-Pedersen, F. (2015). Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast X-ray spectroscopy and ab initio simulations. Physical Review Letters, 114(15), Article 156101. https://doi.org/10.1103/PhysRevLett.114.156101

@article{66cd458c94644bd5a4aa58f0f141b2b7,

title = "Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast X-ray spectroscopy and ab initio simulations",

abstract = "We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.",

author = "H. Xin and J. Larue and H. {\"O}berg and M. Beye and M. Dell'Angela and Turner, {J. J.} and J. Gladh and Ng, {M. L.} and Sellberg, {J. A.} and S. Kaya and G. Mercurio and F. Hieke and D. Nordlund and Schlotter, {W. F.} and Dakovski, {G. L.} and Minitti, {M. P.} and A. F{\"o}hlisch and M. Wolf and W. Wurth and H. Ogasawara and N{\o}rskov, {J. K.} and H. {\"O}str{\"o}m and Pettersson, {L. G.M.} and A. Nilsson and F. Abild-Pedersen",

year = "2015",

doi = "10.1103/PhysRevLett.114.156101",

language = "English",

volume = "114",

journal = "Physical Review Letters",

issn = "0031-9007",

publisher = "American Physical Society",

number = "15",

}

Xin, H, Larue, J, Öberg, H, Beye, M, Dell'Angela, M, Turner, JJ, Gladh, J, Ng, ML, Sellberg, JA, Kaya, S, Mercurio, G, Hieke, F, Nordlund, D, Schlotter, WF, Dakovski, GL, Minitti, MP, Föhlisch, A, Wolf, M, Wurth, W, Ogasawara, H, Nørskov, JK, Öström, H, Pettersson, LGM, Nilsson, A & Abild-Pedersen, F 2015, 'Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast X-ray spectroscopy and ab initio simulations', Physical Review Letters, vol. 114, no. 15, 156101. https://doi.org/10.1103/PhysRevLett.114.156101

TY - JOUR

T1 - Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast X-ray spectroscopy and ab initio simulations

AU - Xin, H.

AU - Larue, J.

AU - Öberg, H.

AU - Beye, M.

AU - Dell'Angela, M.

AU - Turner, J. J.

AU - Gladh, J.

AU - Ng, M. L.

AU - Sellberg, J. A.

AU - Kaya, S.

AU - Mercurio, G.

AU - Hieke, F.

AU - Nordlund, D.

AU - Schlotter, W. F.

AU - Dakovski, G. L.

AU - Minitti, M. P.

AU - Föhlisch, A.

AU - Wolf, M.

AU - Wurth, W.

AU - Ogasawara, H.

AU - Nørskov, J. K.

AU - Öström, H.

AU - Pettersson, L. G.M.

AU - Nilsson, A.

AU - Abild-Pedersen, F.

PY - 2015

Y1 - 2015

N2 - We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.

AB - We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.

U2 - 10.1103/PhysRevLett.114.156101

DO - 10.1103/PhysRevLett.114.156101

M3 - Journal article

AN - SCOPUS:84929590594

SN - 0031-9007

VL - 114

JO - Physical Review Letters

JF - Physical Review Letters

IS - 15

M1 - 156101

ER -

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast X-ray spectroscopy and ab initio simulations

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