Gold Chain Formation via Local Lifting of Surface Reconstruction by Hot Electron Injection on H₂(D₂)/Au(111)

The hexagonal close packed surface of gold shows a 22 × $\sqrt{3}$ "herringbone" surface reconstruction which makes it unique among the (111) surfaces of all metals. This long-range energetically favored dislocation pattern appears in response to the strong tensile stress that would be present on the unreconstructed surface. Adsorption of molecular and atomic species can be used to tune this surface stress and lift the herringbone reconstruction. Here we show that herringbone reconstruction can be controllably lifted in ultrahigh vacuum at cryogenic temperatures by precise hot electron injection in the presence of hydrogen molecules. We use the sharp tip of a scanning tunneling microscope (STM) for charge carrier injection and characterization of the resulting chain nanostructures. By comparing STM images, rotational spectromicroscopy and ab initio calculations, we show that formation of gold atomic chains is associated with release of gold atoms from the surface, lifting of the reconstruction, dissociation of H₂ molecules, and formation of surface hydrides. Gold hydrides grow in a zipper-like mechanism forming chains along the [11̅0] directions of the Au(111) surface and can be manipulated by further electron injection. Finally, we demonstrate that Au(111) terraces can be transformed with nearly perfect terrace selectivity over distances of hundreds of nanometers.