Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra

Research output: ThesisDoctoral Thesis (compilation)

Standard

Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra. / Birgersson, Martin.

Division of Solid State Theory, Lund University, Sölvegatan 14A, S-223 62 Lund, SWEDEN, 2002. 187 p.

Research output: ThesisDoctoral Thesis (compilation)

Harvard

APA

Birgersson, M. (2002). Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra. Division of Solid State Theory, Lund University, Sölvegatan 14A, S-223 62 Lund, SWEDEN,.

CBE

Birgersson M. 2002. Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra. Division of Solid State Theory, Lund University, Sölvegatan 14A, S-223 62 Lund, SWEDEN,. 187 p.

MLA

Birgersson, Martin Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra Division of Solid State Theory, Lund University, Sölvegatan 14A, S-223 62 Lund, SWEDEN,. 2002.

Vancouver

Birgersson M. Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra. Division of Solid State Theory, Lund University, Sölvegatan 14A, S-223 62 Lund, SWEDEN, 2002. 187 p.

Author

Birgersson, Martin. / Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra. Division of Solid State Theory, Lund University, Sölvegatan 14A, S-223 62 Lund, SWEDEN, 2002. 187 p.

RIS

TY - THES

T1 - Calculations of Clean and Adsorbate Covered Metal Surfaces and their Core-Level Photoemission Spectra

AU - Birgersson, Martin

N1 - Defence details Date: 2002-09-30 Time: 13:15 Place: Lecture Hall F, Department of Physics External reviewer(s) Name: Ågren, Hans Title: Prof Affiliation: KTH --- Article: Density-functional theory applied to Rh(111) andCO/Rh(111) systems: geometries, energies and chemical shiftsM. Birgersson, C.-O. Almbladh, M. Borg and J. N. Andersen,submitted to Physical Review B Article: Density-functional theory applied to the CO/Rh(111) system: molecular vibrationsM. Birgersson, C.-O. Almbladh, M. Borg and J. N. Andersen,to be submitted to Physical Review B Article: Effects of core-level degeneracies and crystal fields on core-level spectraM. Birgersson and C.-O. Almbladh,to be submitted to Physical Review B Article: Experimental and theoretical surface core-level shifts of aluminum (100) and (111)M. Borg, M. Birgersson, M. Smedh, A. Mikkelsen, D. L. Adams,R. Nyholm, C.-O. Almbladh and J. N. Andersen,to be submitted to Physical Review B Article: Structure and formation of the Al(100) (sqrt(5) x sqrt(5))R27 Na phase: A LEED, DFT and HRCLS studyM. Borg, A. Mikkelsen, M. Birgersson, M. Smedh, E. Lundgren,D. L. Adams, C.-O. Almbladh and J. N. Andersen,accepted for publication in Surface Science

PY - 2002

Y1 - 2002

N2 - The present thesis is concerned with the theoretical study of x-ray photoemission spectra from clean and adsorbate-covered metal surfaces. The main tool is ab initio density functional (DFT) total energy calculations. The first part gives an overview of the theoretical treatment of x-ray photoemission with our present contributions highlighted, and an introduction to DFT theory and computational techniques for obtaining total energies. The second and main part of the thesis contains the original research papers. In a major part of these, DFT calculations are combined with and compared to experimental photoemission spectra in order to investigate both the local geometric as well as electronic structure. Paper I and II consider clean and CO-covered Rh(111) surfaces, paper IV considers the clean Al(100) and Al(111) surfaces both theoretically and experimentally, and paper V combines experimental techniques and theoretical modeling to investigate the adsorption of Na on Al(100) in a (sqrt(5) x sqrt(5))R27 structure. In all cases we find that ab initio calculations predict the experimental findings well, both with regard to geometries and with regard to chemical shifts and other electronic properties. Furthermore, we find that chemical shifts usually depend on the local geometry in a rather sensitive way. Thus, by combining experiment with theoretical modeling, very precise geometrical information can be obtained. In paper III, we leave the common approximation of treating the core-electron vacancy as a structure-less entity as in the Mahan-Nozières-DeDominicis (MND) model and takes its internal spin and possible orbital angular momentum degrees of freedom into account. We treat the additional symmetry-dependent interactions by leading order cumulant and self energy expansions and apply our theory to both an sp-bonded metal (Al (2p)) as well as 4d metals (Rh (3d), Pd (3d)). In the case of Al and Pd the effects of core-level degeneracy are small, but for Rh we find important modifications. When the effects of core-level degeneracy are included, the theoretical line-shapes agree rather well with experiment.

AB - The present thesis is concerned with the theoretical study of x-ray photoemission spectra from clean and adsorbate-covered metal surfaces. The main tool is ab initio density functional (DFT) total energy calculations. The first part gives an overview of the theoretical treatment of x-ray photoemission with our present contributions highlighted, and an introduction to DFT theory and computational techniques for obtaining total energies. The second and main part of the thesis contains the original research papers. In a major part of these, DFT calculations are combined with and compared to experimental photoemission spectra in order to investigate both the local geometric as well as electronic structure. Paper I and II consider clean and CO-covered Rh(111) surfaces, paper IV considers the clean Al(100) and Al(111) surfaces both theoretically and experimentally, and paper V combines experimental techniques and theoretical modeling to investigate the adsorption of Na on Al(100) in a (sqrt(5) x sqrt(5))R27 structure. In all cases we find that ab initio calculations predict the experimental findings well, both with regard to geometries and with regard to chemical shifts and other electronic properties. Furthermore, we find that chemical shifts usually depend on the local geometry in a rather sensitive way. Thus, by combining experiment with theoretical modeling, very precise geometrical information can be obtained. In paper III, we leave the common approximation of treating the core-electron vacancy as a structure-less entity as in the Mahan-Nozières-DeDominicis (MND) model and takes its internal spin and possible orbital angular momentum degrees of freedom into account. We treat the additional symmetry-dependent interactions by leading order cumulant and self energy expansions and apply our theory to both an sp-bonded metal (Al (2p)) as well as 4d metals (Rh (3d), Pd (3d)). In the case of Al and Pd the effects of core-level degeneracy are small, but for Rh we find important modifications. When the effects of core-level degeneracy are included, the theoretical line-shapes agree rather well with experiment.

KW - chemical shifts

KW - density functional theory

KW - Condensed matter:electronic structure

KW - electrical

KW - magnetic and optical properties

KW - supraconductors

KW - magnetic resonance

KW - relaxation

KW - Atomic and molecular physics

KW - spektroskopi

KW - magnetisk resonans

KW - supraledare

KW - magnetiska och optiska)

KW - egenskaper (elektriska

KW - spectroscopy

KW - Kondenserade materiens egenskaper:elektronstruktur

KW - core-level photoemission

KW - single crystal surfaces

KW - Atom- och molekylärfysik

KW - Fysicumarkivet A:2002:Birgersson

KW - core-hole degeneracies

KW - metal surfaces

KW - adsorption

KW - molecular vibrations

M3 - Doctoral Thesis (compilation)

SN - 91-628-5355-4

PB - Division of Solid State Theory, Lund University, Sölvegatan 14A, S-223 62 Lund, SWEDEN,

ER -