Formation of a High Coverage (3×3) NO Phase on Pd(111) at Elevated Pressures: 
Interplay Between Kinetic and Thermodynamic Accessibility

Ozensoy, Emrah; Hess, Christian; Loffreda, David; Sautet, Philippe; Goodman, D. Wayne

doi:10.1021/jp044264+

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Formation of a High Coverage (3×3) NO Phase on Pd(111) at Elevated Pressures: Interplay Between Kinetic and Thermodynamic Accessibility

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Hess, Christian
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

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Ozensoy, E., Hess, C., Loffreda, D., Sautet, P., & Goodman, D. W. (2005). Formation of a High Coverage (3×3) NO Phase on Pd(111) at Elevated Pressures: Interplay Between Kinetic and Thermodynamic Accessibility. Journal of Physical Chemistry B, 109(12), 5414-5417. doi:10.1021/jp044264+.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0011-094B-6

Abstract

Using in situ polarization modulation infrared reflection absorption spectroscopy and density functional theory calculations, a new high-coverage monomeric NO adsorption state on Pd(111) was observed, and proposed to have a (3x3)-7NO structure. Formation of this high coverage NO phase was found to take place only at elevated pressure and temperature conditions showing that some of the accessible thermodynamic equilibrium states at elevated temperatures and pressures are kinetically hindered at lower temperatures and pressures. Our results emphasize the danger of extrapolating results from traditional surface science experiments performed under ultra-high vacuum to elevated temperature and pressure conditions encountered in heterogeneous catalysis.