Abstract
I describe the production and characterization of isolated hydroxyl species on a Cu(110) surface in this chapter. A hydroxyl group can be produced by the STM-induced dissociation of a water molecule. A hydroxyl can be further dissociated into atomic oxygen. It is found that a hydroxyl has an inclined geometry against the surface normal and switches back and forth between the two orientations via the H atom tunneling. The switching results in the characteristic paired depression aligned along the [001] direction in the STM appearance of hydroxyl. The tunneling switching can be observed directly for a deuterated species (OD) within the time-resolution of STM, while it is smeared out for an OH due to a significant increase of the tunneling rate. The switching is enhanced by the vibrational excitation of the OH(OD) bending mode which is directly associated with the switching reaction coordinate.
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Notes
- 1.
DFT calculations were performed using the STATE code [Y. Morikawa et al. Phys. Rev. B 69, 041403 (2004).]. The OH was put on one side of a three-layer Cu slab arrayed in a 2 × 3 surface unit cell, and the vacuum region of 12.89 Å was inserted between slabs. A GGA-optimized lattice constant of 3.64 Å, which is 0.8 % larger than the experimental value of 3.61 Å, was used to construct the slabs. A (4 × 4) Monkhorst–Pack [H. J. Monkhorst and J. D. Pack, Phys. Rev. B 13, 5188 (1976).] k-point set was used to sample the surface Brillouin zone, and the Fermi level was treated by the first order Methfessel-Paxton scheme [M. Methfessel and A. T. Paxton, Phys. Rev. B 40, 3616 (1989).] with the 0.05 eV smearing width. During the structural optimization, adsorbates and two topmost Cu layers were allowed to relax until the forces on them were less than 0.05 eV/Å.
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Kumagai, T. (2012). Hydroxyl Group: Tunneling Dynamics of Hydrogen Atom. In: Visualization of Hydrogen-Bond Dynamics. Springer Theses, vol 125. Springer, Tokyo. https://doi.org/10.1007/978-4-431-54156-1_7
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