 Contents XV Contents III/42 Physics of Covered Solid Surfaces A: Adsorbed Layers on Surfaces 
Part 5: Adsorption of molecules on metal, 
semiconductor and oxide surfaces 
1 Introduction to physical and chemical properties of adlayer/substrate systems   (H.P. BONZEL) ............................................................................................................................................see subvolume III/42A1 
2 Characterization of adsorbate overlayers: measuring techniques  (CH. WLL)....................................................................................................................................................see subvolume III/42A2 
3 Data: Adsorbate properties 3.1 Adsorption of noble gases 3.1.1 Noble gases on metals and semiconductors (P. ZEPPENFELD)...................see subvolume III/42A1 
3.1.2 Noble gases on graphite, lamellar halides, MgO and NaCl (M. BIENFAIT)..............................................................................................................................................see subvolume III/42A1 
3.2 Adsorption of alkali metals 3.2.1 Alkali metals on metals (R.D. DIEHL, R. McGRATH).........................................see subvolume III/42A1 
3.2.2 Alkali metals on semiconductors (E.G. MICHEL, R. MIRANDA)..... see subvolume III/42A1 3.3 Adsorption of metals 3.3.1 Metals on metals (H. BRUNE)......................................................................................................see subvolume III/42A1 
3.3.2 Metals on semiconductors   (V.G. LIFSHITS, K.OURA, A.A. SARANIN, A.V. ZOTOV)..................................see subvolume III/42A1 
3.4 Non-metallic atomic adsorbates on metals and semiconductors 3.4.1 Adsorbate properties of hydrogen on solid surfaces (K. CHRISTMANN)...................................................... 2 
3.4.1.1 Introduction................................................................................................................................................................................................................2 
3.4.1.2 Some general principles of the hydrogen  surface interaction............................................................................4 
3.4.1.3 The interaction of hydrogen with solid surfaces: experimental data............................................................... 7 
3.4.1.3.1 Adsorption kinetics ............................................................................................................................................................................................ 7 
3.4.1.3.2 Kinetics of hydrogen desorption........................................................................................................................................................19 
3.4.1.3.3 The energetics of hydrogen adsorption and desorption.............................................................................................30 
3.4.1.3.4 The diffusion of adsorbed hydrogen..............................................................................................................................................44 
3.4.1.3.5 The structure of adsorbed hydrogen phases...........................................................................................................................47 
3.4.1.3.6 Vibrational modes of adsorbed hydrogen................................................................................................................................67 
3.4.1.3.7 Electronic states of adsorbed hydrogen and photoemission spectroscopy .............................................85 
3.4.1.3.8 Hydrogen-induced work function changes.............................................................................................................................94 
3.4.1.4 The interaction of hydrogen with solid surfaces: theory........................................................................................100 
3.4.1.4.1 General remarks...............................................................................................................................................................................................100 
3.4.1.4.2 General theories for hydrogen adsorption.............................................................................................................................102 
3.4.1.4.3 Theories covering specific interaction systems...............................................................................................................103 
3.4.1.5 List of acronyms..............................................................................................................................................................................................109 
3.4.1.6 References .............................................................................................................................................................................................................111 
XVI 	 Contents 3.4.2 	Adsorption of C, N, and O on metal surfaces (H. OVER)...............................see subvolume III/42A4 
3.4.3 	Halogens on metals and semiconductors (E.I. ALTMAN) ...............................see subvolume III/42A1 
3.4.4 	Adsorption of S, P, As, Sb and Se on metals, alloys and semiconductors  (M. ENACHESCU, M. SALMERON)............................................................................................see subvolume III/42A3 
3.5 	Surface segregation of atomic species  (H. VIEFHAUS, H.-J. GRABKE, CH. UEBING).................................................................see subvolume III/42A3 
3.6 	Molecules on graphite, BN, MgO (except noble gases) 3.6.1 	Adsorption of molecules on MgO (J. SUZANNE) ....................................................see subvolume III/42A3 
3.6.2 	Adsorption of molecular hydrogen isotopes on graphite and BN (H. WIECHERT)...........................................................................................................................................see subvolume III/42A3 
3.7 	Molecular diatomic adsorbates on metals and semiconductors 3.7.1	CO and N2 adsorption on metal surfaces (A. FHLISCH, H.P. BONZEL) ...........................................
....................................................................................................................................................................................see subvolume III/42A4 
3.7.2 	NO, CN, O2 on metals (W.A. BROWN).............................................................................see subvolume III/42A3 
3.7.3 	Adsorption of diatomic molecules on alloy surfaces   (B. E. NIEUWENHUYS).........................................................................................................................see subvolume III/42A3 
3.8 	Molecular polyatomic adsorbates on metals and semiconductors 3.8.1 	H2O on metals (G. PIRUG, M. MORGENSTERN)................................................................................................................133 
3.8.1.1 	Introduction..........................................................................................................................................................................................................133 
3.8.1.2 	Electronic structure ......................................................................................................................................................................................135 
3.8.1.2.1 	Valence band orbitals and core levels.......................................................................................................................................135 
3.8.1.2.2 	Molecular vibrations...................................................................................................................................................................................136 
3.8.1.2.3 	Work function changes ............................................................................................................................................................................137 
3.8.1.3 	Dissociative versus molecular adsorption.............................................................................................................................138 
3.8.1.4 	Geometric structure of molecularly adsorbed ice..........................................................................................................138 
3.8.1.4.1 	Adsorption geometry..................................................................................................................................................................................138 
3.8.1.4.2 	Binding energy and desorption temperatures....................................................................................................................139 
3.8.1.4.3 	Trapping and sticking ................................................................................................................................................................................140 
3.8.1.4.4 	Diffusion and formation of small clusters.............................................................................................................................141 
3.8.1.4.5 	Ice bilayer...............................................................................................................................................................................................................141 
3.8.1.5 	Tables for 3.8.1.................................................................................................................................................................................................143 
3.8.1.6 	Figures for 3.8.1 ..............................................................................................................................................................................................157 
3.8.1.7 	References for 3.8.1.....................................................................................................................................................................................162 
3.8.2 	H2O and OH on semiconductors (W. JAEGERMANN, T. MAYER) .........see subvolume III/42A4 
3.8.3 	Adsorbate properties of NH3 and PF3 on metals and semiconductors   (E. HASSELBRINK)...................................................................................................................................see subvolume III/42A3 
3.8.4	CO2, NO2, SO2, OCS, N2O, O3 on metal surfaces  (B.E. KOEL, C. PANJA, J. KIM, E. SAMANO) .......................................................................................................................170 
3.8.4.1 	Introduction..........................................................................................................................................................................................................170 
3.8.4.2 	CO2................................................................................................................................................................................................................................171 
3.8.4.2.1 	Structure and bonding of CO2 ...........................................................................................................................................................171 
3.8.4.2.2 	CO2 adsorption on metal surfaces .................................................................................................................................................172 
3.8.4.2.3 	CO2 adsorption on chemically modified metal surfaces.........................................................................................174 
3.8.4.2.4 	CO2 adsorption on alloy surfaces...................................................................................................................................................176 
3.8.4.3 	NO2 ...............................................................................................................................................................................................................................176 

 Contents XVII
3.8.4.3.1 Structure and bonding of NO2...........................................................................................................................................................176 
3.8.4.3.2 NO2 adsorption on metal surfaces.................................................................................................................................................177 
3.8.4.3.3 NO2 adsorption on alloy surfaces ..................................................................................................................................................179 
3.8.4.4 SO2 ................................................................................................................................................................................................................................180 
3.8.4.4.1 Structure and bonding of SO2............................................................................................................................................................180 
3.8.4.4.2 SO2 adsorption on metal surfaces..................................................................................................................................................181 
3.8.4.4.3 SO2 adsorption on metals with coadsorbed alkali metals......................................................................................185 
3.8.4.3.4 SO2 adsorption on alloy surfaces ...................................................................................................................................................186 
3.8.4.5 OCS..............................................................................................................................................................................................................................186 
3.8.4.5.1 Structure and bonding of OCS .........................................................................................................................................................186 
3.8.4.5.2 OCS adsorption on metal surfaces................................................................................................................................................186 
3.8.4.6 N2O ...............................................................................................................................................................................................................................187 
3.8.4.6.1 Structure and bonding of N2O...........................................................................................................................................................187 
3.8.4.6.2 Adsorption of N2O on metal surfaces........................................................................................................................................187 
3.8.4.6.3 N2O adsorption on alloy surfaces ..................................................................................................................................................190 
3.8.4.7 O3....................................................................................................................................................................................................................................190 
3.8.4.7.1 Structure and bonding of O3 ...............................................................................................................................................................190 
3.8.4.7.2 O3 adsorption on metal surfaces......................................................................................................................................................191 
3.8.4.7.3 O3 adsorption on alloy surfaces.......................................................................................................................................................191 
3.8.4.7.4 O3 adsorption on metal oxide surfaces.....................................................................................................................................192 
3.8.4.8 Tables for 3.8.4.................................................................................................................................................................................................192 
3.8.4.9 Figures for 3.8.4 ..............................................................................................................................................................................................217 
3.8.4.10 References for 3.8.4.....................................................................................................................................................................................235 
3.8.5 Substituted hydrocarbons on metals  (W.T. TYSOE, D.R. MULLINS) ........................................................................... see subvolume III/42A3 
3.8.6 Adsorbate properties of linear hydrocarbons  (G. RUPPRECHTER, G.A. SOMORJAI)............................................................................................................................................243 
3.8.6.1 Introduction..........................................................................................................................................................................................................243 
3.8.6.1.1 General considerations..............................................................................................................................................................................243 
3.8.6.1.2 Experimental aspects..................................................................................................................................................................................244 
3.8.6.1.3 List of symbols and abbreviations ................................................................................................................................................245 
3.8.6.2 Reviews....................................................................................................................................................................................................................246 
3.8.6.3 Alkanes.....................................................................................................................................................................................................................248 
3.8.6.3.1 Methane CH4.......................................................................................................................................................................................................248 
3.8.6.3.2 Ethane C2H6 .........................................................................................................................................................................................................254 
3.8.6.3.3 Propane C3H8......................................................................................................................................................................................................256 
3.8.6.3.4 Butane C4H10.......................................................................................................................................................................................................257 
3.8.6.3.5 Pentanes C5H12 and higher alkanes..............................................................................................................................................258 
3.8.6.3.6 Various (Hydrocarbon fragments, Radicals, etc) ..........................................................................................................259 
3.8.6.4 Alkenes.....................................................................................................................................................................................................................262 
3.8.6.4.1 Ethylene C2H4 and Ethylidyne C2H3 ..........................................................................................................................................264 
3.8.6.4.2 Propene C3H6......................................................................................................................................................................................................276 
3.8.6.4.3 Butenes C4H10....................................................................................................................................................................................................278 
3.8.6.4.4 Pentenes C5H10 and Hexenes C6H12 ............................................................................................................................................282 
3.8.6.5 Dienes ........................................................................................................................................................................................................................283 
3.8.6.5.1 Propadiene C3H4..............................................................................................................................................................................................283 
3.8.6.5.2 Butadiene C4H6.................................................................................................................................................................................................283 
3.8.6.5.3 Pentadiene C5H8, Hexadiene C6H10.............................................................................................................................................285 
3.8.6.6 Alkynes.....................................................................................................................................................................................................................285 
3.8.6.6.1 Acetylene C2H2.................................................................................................................................................................................................286 
3.8.6.6.2 Propyne C3H4 .....................................................................................................................................................................................................292 

XVIII 	 Contents 3.8.6.7 	Tables for 3.8.6.................................................................................................................................................................................................295 
3.8.6.8 	References for 3.8.6.....................................................................................................................................................................................320 
3.8.7 	Cyclic hydrocarbons (G. HELD, H.P. STEINRCK) .................................................see subvolume III/42A4 
3.8.8	Oxygenated hydrocarbons on metals and semiconductors (J. VOHS)...see subvolume III/42A3 3.8.9 	Halogen-substituted hydrocarbons on metals and semiconductors  (J. FIEBERG, J.W. WHITE) ................................................................................... see subvolume III/42A3 
3.8.10	Polyatomic chain-like hydrocarbons on metals and semiconductors (W. ECK).......................................
 ....................................................................................................................................................................................see subvolume III/42A4 
3.9 	Adsorption on oxides (H. KUHLENBECK, H.J. FREUND) .........................................................................................332 
3.9.1 	Introduction..........................................................................................................................................................................................................332 
3.9.2 	Abbreviations used in the text...........................................................................................................................................................332 
3.9.3 	Al2O3 ...........................................................................................................................................................................................................................334 
3.9.3.1 	CO adsorption....................................................................................................................................................................................................335 
3.9.3.2 	H2O adsorption .................................................................................................................................................................................................335 
3.9.4 	CaO...............................................................................................................................................................................................................................335 
3.9.4.1 	CO2 adsorption..................................................................................................................................................................................................336 
3.9.4.2 	H2O adsorption .................................................................................................................................................................................................336 
3.9.4.3 	SO2 adsorption ..................................................................................................................................................................................................336 
3.9.5 	CeO2.............................................................................................................................................................................................................................336 
3.9.5.1 	CO adsorption on CeO2(111).............................................................................................................................................................337 
3.9.5.2 	H2O and D2O adsorption on CeO2(001) and CeO2(111) .......................................................................................337 
3.9.6 	a-Cr2O3.....................................................................................................................................................................................................................338 
3.9.6.1 	CO adsorption....................................................................................................................................................................................................339 
3.9.6.2 	NO adsorption ...................................................................................................................................................................................................340 
3.9.6.3 	CO2 adsorption..................................................................................................................................................................................................340 
3.9.6.4 	O2 adsorption......................................................................................................................................................................................................340 
3.9.6.5 	H2O adsorption .................................................................................................................................................................................................341 
3.9.7 	CoO ..............................................................................................................................................................................................................................341 
3.9.7.1 	CO adsorption....................................................................................................................................................................................................342 
3.9.7.2 	NO adsorption ...................................................................................................................................................................................................342 
3.9.7.3 	H2O adsorption .................................................................................................................................................................................................342 
3.9.8 	Cu2O ............................................................................................................................................................................................................................343 
3.9.8.1 	CO adsorption....................................................................................................................................................................................................344 
3.9.8.2 	H2O adsorption .................................................................................................................................................................................................344 
3.9.8.3 	CH3OH adsorption........................................................................................................................................................................................344 
3.9.8.4 	O2 adsorption......................................................................................................................................................................................................344 
3.9.9 	FeO, Fe3O4 and a-Fe2O3.........................................................................................................................................................................345 
3.9.9.1 	Ethylbenzene, water and styrene adsorption ......................................................................................................................347 
3.9.10 	MgO.............................................................................................................................................................................................................................350 
3.9.10.1 	H2O adsorption .................................................................................................................................................................................................353 
3.9.10.2 	CO adsorption....................................................................................................................................................................................................354 
3.9.10.3 	CO2 adsorption..................................................................................................................................................................................................354 
3.9.11 	NiO ...............................................................................................................................................................................................................................355 
3.9.11.1 	CO adsorption....................................................................................................................................................................................................359 
3.9.11.2 	NO adsorption ...................................................................................................................................................................................................359 
3.9.11.3 	H2O adsorption .................................................................................................................................................................................................361 
3.9.11.4 	HCOOH adsorption on NiO(111).................................................................................................................................................362 
3.9.11.5 	H2 adsorption on NiO(100)..................................................................................................................................................................363 
3.9.11.6 	H2S adsorption on NiO(100) ..............................................................................................................................................................363 
3.9.11.7 	CO2 adsorption on NiO(111) .............................................................................................................................................................363 
3.9.12 	RuO2 ............................................................................................................................................................................................................................363 

 Contents XIX
3.9.12.1 CO adsorption....................................................................................................................................................................................................364 
3.9.13 SnO2.............................................................................................................................................................................................................................365 
3.9.13.1 O2 adsorption......................................................................................................................................................................................................366 
3.9.13.2 H2O adsorption .................................................................................................................................................................................................366 
3.9.13.3 CH3OH adsorption........................................................................................................................................................................................366 
3.9.13.4 HCOOH adsorption .....................................................................................................................................................................................366 
3.9.14 TiO2 ..............................................................................................................................................................................................................................366 
3.9.14.1 CO adsorption....................................................................................................................................................................................................370 
3.9.14.2 H2O adsorption .................................................................................................................................................................................................372 
3.9.14.3 HCOOH adsorption .....................................................................................................................................................................................372 
3.9.14.4 CH3COOH adsorption...............................................................................................................................................................................375 
3.9.15 V2O3.............................................................................................................................................................................................................................376 
3.9.15.1 O2 adsorption......................................................................................................................................................................................................376 
3.9.15.2 H2O adsorption .................................................................................................................................................................................................376 
3.9.16 V2O5.............................................................................................................................................................................................................................377 
3.9.16.1 CO and SO2 adsorption............................................................................................................................................................................377 
3.9.16.2 H2 and H adsorption ....................................................................................................................................................................................377 
3.9.17 ZnO...............................................................................................................................................................................................................................378 
3.9.17.1 CO adsorption....................................................................................................................................................................................................380 
3.9.17.2 CO2 adsorption..................................................................................................................................................................................................381 
3.9.17.3 CH3OH adsorption........................................................................................................................................................................................381 
3.9.17.4 HCOOH adsorption .....................................................................................................................................................................................382 
3.9.18 Tables of selected adsorbate properties...................................................................................................................................382 
3.9.19 References for 3.9..........................................................................................................................................................................................389 
3.10 Surface diffusion on metals, semiconductors, and insulators   (E.G. SEEBAUER, M.Y.L. JUNG) ...............................................................................................see subvolume III/42A1 
4 Data: Adsorbate-induced changes of substrate properties 4.1 Surface structure on metals and semiconductors   (M.A. VAN HOVE, K. HERMANN, P.R. WATSON) .................................................see subvolume III/42A2 
4.2 Electron work function of metals and semiconductors (K. JAKOBI)...see subvolume III/42A2 4.3 Adsorbate induced surface core level shifts of metals  (R. DENECKE, N. M.RTENSSON).............................................................................................see subvolume III/42A4 
4.4 Surface free energy and surface stress (D. SANDER, H. IBACH)...............see subvolume III/42A2 
4.5 Surface phonon dispersion (M.A. ROCCA) ........................ see subvolume III/42A2 

