Ammonia adsorbed on Cu(110): An angle resolved x-ray spectroscopic and ab initio study

We present a study of a monolayer of ammonia (NH3) adsorbed on Cu(110) using core level spectroscopies in combination with ab initio calculations based on density functional theory. In particular, x-ray emission spectroscopy has been applied, providing an unsurpassed view of the electronic structure of NH3 upon adsorption. The saturated NH3 monolayer, Θ∼0.4 ML, is found to induce strong adsorbate–adsorbate interaction, causing the molecules to tilt on the surface. Based on the angular distribution of the x-ray emission (XE) spectra, we have been able to estimate a mean tilt angle from the surface normal of 40°–45° for the saturated monolayer; the accompanying theoretical calculations for up to three NH3 molecules on a Cu21 all-electron cluster model support a tilted structure due to adsorbate–adsorbate dipole, and possibly hydrogen bonding, interactions. Since the creation of a core hole on the nitrogen atom site in the intermediate state of the XE process does not affect the symmetry of the molecule, a s...

[1]  J. Stöhr,et al.  The adsorption structure of glycine adsorbed on Cu(110); comparison with formate and acetate/Cu(110) , 1998 .

[2]  J. Stöhr,et al.  Nature of the surface chemical bond in N-2 On Ni(100) studied by x-ray-emission spectroscopy and ab initio calculations , 1998 .

[3]  D. P. Woodruff,et al.  Determination of the local structure of glycine adsorbed on Cu(110) , 1998 .

[4]  D. P. Woodruff,et al.  Structure determination of ammonia on Cu(110) — a low-symmetry adsorption site , 1997 .

[5]  D. Mocuta,et al.  Adsorption and electron-stimulated dissociation of ammonia on Cu(110): an ESDIAD study , 1997 .

[6]  J. Stöhr,et al.  An atom-specific look at the surface chemical bond , 1997 .

[7]  M. P. Sears,et al.  Ab initio calculations of adsorbate hydrogen-bond strength : ammonia on Pt(111) , 1996 .

[8]  D. P. Woodruff,et al.  Quantitative structure determination of an NHx species adsorbed on Cu(110) , 1996 .

[9]  S. Lunell,et al.  Manifestation of the paramagnetic splitting of physisorbed O2 in core and valence spectroscopies , 1996 .

[10]  Nilsson,et al.  Direct probing of the adsorbate-substrate chemical bond using angle-dependent x-ray-emission spectroscopy. , 1995, Physical review. B, Condensed matter.

[11]  P. A. Brühwiler,et al.  A very high resolution electron spectrometer , 1994 .

[12]  Sandell,et al.  Resonant Auger studies of CO adsorbed on two groups of d transition metals. , 1994, Physical review. B, Condensed matter.

[13]  A. Jansen,et al.  The oxidation of ammonia by copper , 1993 .

[14]  A. Jansen,et al.  Dissociation of ammonia on a copper surface and the effect of oxygen coadsorption: a quantum-chemical study , 1993 .

[15]  M. W. Roberts,et al.  Reaction pathways in the oxydehydrogenation of ammonia at Cu(110) surfaces , 1993 .

[16]  Chen,et al.  K-shell excitation of the water, ammonia, and methane molecules using high-resolution photoabsorption spectroscopy. , 1993, Physical review. A, Atomic, molecular, and optical physics.

[17]  Sandell,et al.  Higher excited states in x-ray-absorption spectra of adsorbates. , 1993, Physical review. B, Condensed matter.

[18]  O. Björneholm,et al.  Orientation of a molecular precursor: a NEXAFS study of O2/Ag(110) , 1992 .

[19]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[20]  O. Björneholm,et al.  Photoabsorption and the unoccupied partial density of states of chemisorbed molecules , 1992 .

[21]  D. P. Woodruff,et al.  The effect of anisotropic molecular vibrations in photoelectron diffraction of adsrobed species , 1992 .

[22]  A. Jansen,et al.  Chemisorption theory of ammonia on copper , 1992 .

[23]  Per E. M. Siegbahn,et al.  Electronic shell closings in metal cluster plus adsorbate systems: Cu+7CO and Cu+17CO , 1991 .

[24]  S. Kevan,et al.  Isothermal coverage dependent measurements of NH3 and ND3 desorption from Cu(001) , 1991 .

[25]  Hong Yang,et al.  Adsorption of ammonia on nickel(111) , 1990 .

[26]  D. Salahub,et al.  New algorithm for the optimization of geometries in local density functional theory , 1990 .

[27]  R. Madix,et al.  Cleavage of N-H bonds by active oxygen on Ag(110): I. Ammonia , 1989 .

[28]  J. Rubensson,et al.  Soft x-ray emission spectroscopy using monochromatized synchrotron radiation (invited) , 1989 .

[29]  P. Siegbahn,et al.  On the cluster convergence of chemisorption energies , 1988 .

[30]  J. Stöhr,et al.  Determination of molecular orientations on surfaces from the angular dependence of near-edge x-ray-absorption fine-structure spectra. , 1987, Physical review. B, Condensed matter.

[31]  Wahlgren,et al.  Model studies of the chemisorption of hydrogen and oxygen on Cu(100). , 1987, Physical review. B, Condensed matter.

[32]  Hermann,et al.  New analysis of lone-pair binding-energy shifts in photoemission from adsorbed molecules: CO and NH3 on Cu(100). , 1986, Physical review. B, Condensed matter.

[33]  J. Yates,et al.  NH3 adsorption on Ni(110) and the production of the NH2 species by electron irradiation , 1985 .

[34]  T. Madey,et al.  Influence of surface additives (Na and O) on the adsorption and structure of NH3, on Ni(110) , 1985 .

[35]  Klaus Hermann,et al.  On the nature of the bonding of lone pair ligands to a transition metal , 1984 .

[36]  Marvin L. Cohen,et al.  Electronic structure of solids , 1984 .

[37]  Paul S. Bagus,et al.  A new analysis of charge transfer and polarization for ligand–metal bonding: Model studies of Al4CO and Al4NH3 , 1984 .

[38]  T. Madey,et al.  Adsorption and orientation of NH3 on Ru(001) , 1983 .

[39]  D. A. King,et al.  The Chemical Physics of Solid Surfaces and Heterogeneous Catalysis , 1981 .

[40]  G. Fisher.  The electronic structure of two forms of molecular ammonia adsorbed on Pt(111) , 1981 .

[41]  U. V. Barth,et al.  The effect of the core hole on x-ray emission spectra in simple metals , 1979 .

[42]  William L. Jorgensen,et al.  The Organic Chemist's Book of Orbitals , 1973 .

[43]  L. Karlsson,et al.  Analysis of vibrational structure and Jahn‐Teller effects in the electron spectrum of ammonia , 1973 .

[44]  R. Manne.  Molecular Orbital Interpretation of X‐Ray Emission Spectra: Simple Hydrocarbons and Carbon Oxides , 1970 .

[45]  A. Wachters,et al.  Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms , 1970 .

[46]  C. Campbell,et al.  A quantum-chemical study of the adsorption of water, formaldehyde and ammonia on copper surfaces and water on ZnO(0001) , 1988 .

[47]  G. Ertl.  Surface Science and Catalysis—Studies on the Mechanism of Ammonia Synthesis: The P. H. Emmett Award Address , 1980 .

[48]  C. E. Brion,et al.  K-shell excitation of CH4, NH3, H2O, CH3OH, CH3OCH3 and CH3NH2 by 2.5 keV electron impact , 1974 .