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Formation of Unique Trimer of NO on Cu(111)

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Reactivity of Nitric Oxide on Copper Surfaces

Part of the book series: Springer Theses ((Springer Theses))

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Abstract

In this chapter, the unexpected formation of a NO trimer on Cu(111) is reported. Using STM at 6 K, the NO molecule was found to be bonded to the fcc hollow site in an upright configuration. The individual NO molecule is imaged as a ring-like protrusion, which is characteristic of the doubly degenerate \(2\pi ^*\) orbital. The triangular trimer is thermodynamically more favorable than a monomer or a dimer, and its bonding structure was characterized by STM manipulation. This unique behavior of NO on Cu(111) is ascribed to the threefold symmetry of the surface, facilitating the effective mixing of the \(2\pi ^*\) orbitals in a triangular configuration.

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Notes

  1. 1.

    For Cu(111), 1 ML \(= 1.76 \times 10^{15}\) molecules/cm\(^{2}\).

  2. 2.

    Applying a further voltage pulse of 0.5 eV to the trimer in Fig. 8.4e induced molecular diffusion and rotation yielding the original trimer (Fig. 8.4d).

  3. 3.

    The diagrams are not calculated but depicted for qualitative argument of the orbital mixing. A series of orbitals for the dimer are depicted according to that for gas-phase (NO)\(_2\) [14, 15]. The molecular orbitals for (NO)\(_3\) are illustrated by reference to 2p orbitals of three C atoms for cyclopropane [16].

  4. 4.

    The STM image (Fig. 8.3b) of the dimer shows two protrusions with inequivalent apparent heights. As the adsorption site of the dimer shows \(C_\mathrm {s}\) symmetry (Fig. 8.3c–e), the geometry and/or electronic state of the dimer are/is asymmetric relative to the molecular plane.

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  1. The University of Tokyo, Kashiwa, Chiba, Japan

    Akitoshi Shiotari

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  1. Akitoshi Shiotari
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Shiotari, A. (2017). Formation of Unique Trimer of NO on Cu(111). In: Reactivity of Nitric Oxide on Copper Surfaces. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-10-4582-0_8

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