First-principles investigation forM(CO)n/Ag(110)(M=Fe,Co, Ni, Cu, Zn, and Ag;n=1,2) systems: Geometries, STM images, and vibrational frequencies

Abstract

Fe, Cu atoms and CO molecules were manipulated with a scanning tunneling microscope (STM) on a Ag(110) surface, and one or two CO can transfer from the surface and bond with a metal atom through the STM tip [H. J. Lee and W. Ho, Science 286, 1719 (1999); Phys. Rev. B 61, R16347 (2000)]. We perform a density-functional cluster model investigation for the systems. The experimental geometries are validated and understood using the frontier orbital theory. The STM topographic images are reproduced. The vibrational frequencies of the adsorbate systems are obtained by diagonalizing the second-derivative matrices and are in excellent agreement with the experimental measurements. The geometries and C-O stretch frequencies are predicted for systems with the adsorbate metal atom being Co, Ni, Zn, and Ag. These systems can be divided to two classes, and each class exhibits a different set of properties.