XVI	Contents 
Contents 
III/42 Physics of Covered Solid Surfaces 
A: Adsorbed Layers on Surfaces Part 3: Surface Segregation and Adsorption on Surfaces 
1	Introduction to physical and chemical properties of adlayer/substrate systems 
(H.P. BONZEL) ...................................................

2	Characterization of adsorbate overlayers: measuring techniques (CH. WLL) ..................................................... 
3	Data: Adsorbate properties 
3.1	Adsorption of noble gases 

3.1.1	Noble gases on metals and semiconductors (P. ZEPPENFELD).......

3.1.2	Noble gases on graphite, lamellar halides, MgO and NaCl 

(M. BIENFAIT)....................................................

3.2	Adsorption of alkali metals 

3.2.1	Alkali metals on metals (R.D. DIEHL, R. McGRATH) ...............

3.2.2	Alkali metals on semiconductors (E.G. MICHEL, R. MIRANDA)..... 
3.3	Adsorption of metals 

3.3.1	Metals on metals (H. BRUNE) .....................................

3.3.2	Metals on semiconductors 

(V.G. LIFSHITS, K.OURA, A.A. SARANIN, A.V. ZOTOV) ............

3.4	Non-metallic atomic adsorbates on metals and semiconductors 
3.4.1	Chemisorbed hydrogen on metals and semiconductors 

(K. CHRISTMANN) ...............................................

3.4.2	C, N, O on metals and semiconductors (H. OVER) ................

3.4.3	Halogens on metals and semiconductors (E.I. ALTMAN) ..........

see subvolume III/42A1 
see subvolume III/42A2 
see subvolume III/42A1 see subvolume III/42A1 see subvolume III/42A1 see subvolume III/42A1 see subvolume III/42A1 see subvolume III/42A1 
see subvolume III/42A4 see subvolume III/42A4 see subvolume III/42A1 

3.4.4 P, S, As, Sb on metals and semiconductors (M. ENACHESCU, M. SALMERON) ............ 2
3.4.4.1 Introduction........................................................................................................................................................................................................ 2
3.4.4.2 Adsorption of S on metals..................................................................................................................................................................... 2
3.4.4.3 Adsorption of P on metals and semiconductors.............................................................................................................30
3.4.4.4 Adsorption of As on semiconductors....................................................................................................................................... 32
3.4.4.5 Adsorption of Se on metals and semiconductors ..........................................................................................................34
3.4.4.6 Adsorption of Sb on semiconductors....................................................................................................................................... 36
3.4.4.7 Figures for 3.4.4.......................................................................................................................................................................................... 40
3.4.4.8 References for 3.4.4................................................................................................................................................................................. 50
3.5 Surface segregation of atomic species (H. VIEFHAUS, H.-J. GRABKE, CH. UEBING)....... 62
3.5.1 Introduction..................................................................................................................................................................................................... 62
3.5.2 Theories of surface segregation.................................................................................................................................................... 63
3.5.3 Experimental data on surface segregation...........................................................................................................................71
3.5.3.1 Surface segregation of nonmetallic solutes on metals..............................................................................................71
3.5.3.2 Surface segregation of metals on metals...............................................................................................................................82
3.5.4 List of tables................................................................................................................................................................................................... 88
Contents XVII 
3.5.5 Figures for 3.5............................................................................................................................................................................................ 112
3.5.6 References for 3.5................................................................................................................................................................................... 123
3.6 Molecules on graphite, BN, MgO (except noble gases) 3.6.1 Adsorption of molecules on MgO (J. SUZANNE) .......................................................................................................134
3.6.1.1 Introduction.................................................................................................................................................................................................. 134
3.6.1.2 Experimental techniques .................................................................................................................................................................. 136
3.6.1.3 Calculations and simulations........................................................................................................................................................ 140
3.6.1.4 Simple molecules.................................................................................................................................................................................... 141
3.6.1.5 Hydrocarbon molecules .................................................................................................................................................................... 144
3.6.1.6 Ammonia and water.............................................................................................................................................................................. 147
3.6.1.7 Other molecules........................................................................................................................................................................................ 149
3.6.1.8 Figures for 3.6.1....................................................................................................................................................................................... 151
3.6.1.9 References for 3.6.1.............................................................................................................................................................................. 157
3.6.2 Adsorption of molecular hydrogen isotopes on graphite and BN (H. WIECHERT) .....................162
3.6.2.1 Introduction.................................................................................................................................................................................................. 162
3.6.2.2 Properties of the substrates: graphite and BN...............................................................................................................163
3.6.2.3 Coverage calibration............................................................................................................................................................................ 166
3.6.2.4 Molecular properites of the hydrogens................................................................................................................................ 167
3.6.2.5 Interaction potentials, law of corresponding states and search for a superfluid phase ............169
3.6.2.6 Adsorption isotherms and thermodynamic properties...........................................................................................174
3.6.2.7 Monolayer phase diagrams............................................................................................................................................................. 179
3.6.2.7.1 Phase diagrams of para-H2, HD, ortho-D2 for T > 1 K.........................................................................................179
3.6.2.7.2 Phase diagrams of ortho-H2, para-D2 on graphite; para-ortho hydrogen on BN for T < 2 K.................................................................................................................................................................................. 185
3.6.2.7.3 Phase diagram of D2 on Kr preplated graphite.............................................................................................................191
3.6.2.8 Phase transitions and critical behavior ................................................................................................................................ 193
3.6.2.8.1 Theoretical background of the order-disorder transition....................................................................................193
3.6.2.8.2 Experimental results for the critical behavior H2, HD, D2 adsorbed on graphite near the critical and tricritical point............................................................................................................................................................. 196
3.6.2.8.3 Experimental results for the critical behavior of D2 on Kr preplated graphite in the vicinity of the critical and tricritical point........................................................................................................................200
3.6.2.8.4 Survey of theoretical concepts on the commensurate-incommensurate transition ......................203
3.6.2.8.5 Computer simulation studies on the commensurate-incommensurate transition...........................210
3.6.2.8.6 Survey of theories on epitaxial rotation phenomena...............................................................................................213
3.6.2.8.7 Commensurate-incommensurate transition of H2, HD, D2 physisorbed on graphite.................215
3.6.2.8.8 The a phase.................................................................................................................................................................................................. 222
3.6.2.8.9 The . phase and its derivatives................................................................................................................................................... 224
3.6.2.8.10 The reentrant fluid phase and the isotropic fluid phase .......................................................................................229
3.6.2.8.11 Solid H2-D2 mixtures........................................................................................................................................................................... 234
3.6.2.8.12 The incommensurate phase and the melting transition.........................................................................................234
3.6.2.8.13 The commensurate-incommensurate transition of D2 on Kr preplated graphite............................236
3.6.2.9 Dynamics of H2, HD, D2 monolayers physisorbed on graphite....................................................................238
3.6.2.10 Properties of H2, HD, D2 multilayers on graphite .....................................................................................................244
3.6.2.12 Tables for 3.6.2......................................................................................................................................................................................... 256
3.6.2.13 References for 3.6.2.............................................................................................................................................................................. 279
3.7 Molecular diatomic adsorbates on metals and semiconductors 

3.7.1 CO and N2 on metals (A. FHLISCH, A. NILSSON, H.P. BONZEL) ... see subvolume III/42A4 
3.7.2 NO, CN, O2 on metals (W.A. BROWN) ................................................298
3.7.2.1 Introduction.................................................................................................................................................................................................. 298
XVIII Contents 

3.7.2.2 NO adsorption on metal surfaces.............................................................................................................................................. 300
3.7.2.3 CN adsorption on metal surfaces.............................................................................................................................................. 320
3.7.2.4 Molecular O2 adsorption on surfaces.................................................................................................................................... 326
3.7.2.5 Figures for 3.7.2....................................................................................................................................................................................... 337
3.7.3 Diatomic molecules on alloys (B. E. NIEUWENHUYS) ..................................358
3.7.3.1 Introduction.................................................................................................................................................................................................. 358
3.7.3.2 Adsorption properties of well defined bimetallic surfaces................................................................................360
3.7.3.2.1 Ni-Al surfaces ............................................................................................................................................................................................ 361
3.7.3.2.2 Ni-Fe surfaces............................................................................................................................................................................................ 362
3.7.3.2.3 Ni-Cu and Ni-Au surfaces............................................................................................................................................................... 362
3.7.3.2.4 Ni-W surfaces............................................................................................................................................................................................. 363
3.7.3.2.5 Cu-Au surfaces.......................................................................................................................................................................................... 363
3.7.3.2.6 Ru-Cu and Ru-Au surfaces............................................................................................................................................................. 363
3.7.3.2.7 Pd-Cu surfaces........................................................................................................................................................................................... 364
3.7.3.2.8 Pd-Ag surfaces........................................................................................................................................................................................... 366
3.7.3.2.9 Pd-Au surfaces........................................................................................................................................................................................... 367
3.7.3.2.10 Other Pd alloy surfaces...................................................................................................................................................................... 367
3.7.3.2.11 Pt-Ti surfaces.............................................................................................................................................................................................. 368
3.7.3.2.12 Pt-Fe surfaces............................................................................................................................................................................................. 369
3.7.3.2.13 Pt-Co surfaces............................................................................................................................................................................................ 370
3.7.3.2.14 Pt-Ni surfaces ............................................................................................................................................................................................. 371
3.7.3.2.15 Pt-Cu surfaces............................................................................................................................................................................................ 373
3.7.3.2.16 Pt-Ge surfaces............................................................................................................................................................................................ 374
3.7.3.2.17 Pt-Ru surfaces............................................................................................................................................................................................ 374
3.7.3.2.18 Pt-Rh surfaces............................................................................................................................................................................................ 375
3.7.3.2.19 Pt-Sn surfaces............................................................................................................................................................................................. 376
3.7.3.2.20 Pt-La surfaces............................................................................................................................................................................................. 378
3.7.3.2.21 Pt-Re surfaces............................................................................................................................................................................................. 378
3.7.3.3 References for 3.7.3.............................................................................................................................................................................. 379
3.7.4 Diatomic molecules on semiconductors (K. HORN) ................ see subvolume III/42A4

3.8 Molecular polyatomic adsorbates on metals and semiconductors 

3.8.1 H2O and OH on metals (G. PIRUG) ............................... see subvolume III/42A4

3.8.2 H2O and OH on semiconductors (W. JAEGERMANN, T. MAYER) ... see subvolume III/42A4 
3.8.3 NH3 and PF3 on metals and semiconductors (E. HASSELBRINK).................................................................384
3.8.3.1 NH3 ...................................................................................................................................................................................................................... 384
3.8.3.1.1 Adsorption on metals........................................................................................................................................................................... 384
3.8.3.1.2 Adsorption on semiconductors................................................................................................................................................... 392
3.8.3.2 PF3 ........................................................................................................................................................................................................................ 393
3.8.3.3 References for 3.8.3.............................................................................................................................................................................. 396
3.8.4 CO2, NO2, SO2, OCS, N2O, O3 (B.E. KOEL) ...................... see subvolume III/42A4

3.8.5 Substituted hydrocarbons on metals (W.T. TYSOE, D.R. MULLINS) ....................399
3.8.5.1 Background .................................................................................................................................................................................................. 399
3.8.5.2 Methylthiolates on metal surfaces............................................................................................................................................ 399
3.8.5.3 Methylamine on metal surfaces.................................................................................................................................................. 406
3.8.5.4 Acetonitrile and methyl isocyanide on metal surfaces..........................................................................................411
3.8.5.5 Nitromethane and methyl nitride on metal surfaces................................................................................................415
3.8.5.6 References for 3.8.5.............................................................................................................................................................................. 418
Contents XIX 
3.8.6 Linear hydrocarbons and CH4 on metals and semiconductors 

(G. SOMORJAI, G. RUPPRECHTER)................................. see subvolume III/42A4

3.8.7 Cyclic hydrocarbons on metals and semiconductors 

(G. HELD, H.P. STEINRCK) ...................................... see subvolume III/42A4

3.8.8 Oxygenated hydrocarbons on metals and semiconductors (J. VOHS) ..................... 422
3.8.8.1 Introduction.................................................................................................................................................................................................. 422
3.8.8.2 Alcohols........................................................................................................................................................................................................... 423
3.8.8.3 Aldehydes and ketones....................................................................................................................................................................... 423
3.8.8.4 Carboxylic acids....................................................................................................................................................................................... 424
3.8.8.5 Epoxides.......................................................................................................................................................................................................... 424
3.8.8.6 Tables for 3.8.8......................................................................................................................................................................................... 425
3.8.8.7 References for 3.8.8.............................................................................................................................................................................. 436
3.8.9 Halogen-substituted hydrocarbons on metals and semiconductors (J. FIEBERG, J.W. WHITE) ............................................................440
3.8.9.1 Introduction.................................................................................................................................................................................................. 440
3.8.9.2 Data...................................................................................................................................................................................................................... 442
3.8.9.2.1 Halogen substituted hydrocarbons on metals................................................................................................................442
3.8.9.2.2 Halogen substituted hydrocarbons on semiconductors.........................................................................................471
3.8.9.3 References for 3.8.9.............................................................................................................................................................................. 476
3.8.10 Polyatomic chain-like hydrocarbons on metals and semiconductors 

(M. GRUNZE) .................................................... see subvolume III/42A4

3.8.11 Large aromatic adsorbates on metals and semiconductors 

(M. SOKOLOWSKI, E. UMBACH) .................................. see subvolume III/42A4

3.9 Adsorption on oxides (H. KUHLENBECK, H.J. FREUND) ............ see subvolume III/42A4

3.10 Adsorption on alkali halides (J. HEIDBERG) ....................... see subvolume III/42A4

3.11 Surface diffusion on metals, semiconductors, and insulators 

(E.G. SEEBAUER, M.Y.L. JUNG) .................................. see subvolume III/42A1

3.12 Dynamics of activated adsorption (A.C. LUNTZ) .................. see subvolume III/42A4

4 Data: Adsorbate-induced changes of substrate properties .......... see subvolume III/42A2

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 Electron binding energy of metals and semiconductors 

(R. DENECKE, N. MARTENSSON, A. NILSSON)..................... 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

4.6 Surface optical properties (N. ESSER, W. RICHTER)................ see subvolume III/42A4


