Free ebooks ==> www.Ebook777.com www.Ebook777.com Free ebooks ==> www.Ebook777.com Elementary Physicochemical Processes on Solid Surfaces www.Ebook777.com FUNDAMENTAL AND APPLIED CATALYSIS Series Editors: M V Twigg Imperial Chemical Industries P.L.C Billingham, Cleveland, United Kingdom M S Spencer School oj Chemistry and Applied Chemistry University oj Wales College oJCardifJ Cardiff, United Kingdom CATALYTIC AMMONIA SYNTHESIS: Fundamentals and Practice Edited by J R Jennings CATAL YST CHARACTERIZATION: Physical Techniques for Solid Materials Edited by Boris Imelik and Jacques C Vedrine ELEMENTARY PHYSICOCHEMICAL PROCESSES ON SOLID SURFACES V P Zhdanov PRINCIPLES OF CATAL YST DEVELOPMENT James T Richardson A Continuation Order Plan is available for this series A continuation order will bring delivery of each new volume immediately upon publication Volumes are billed only upon actual shipment For further information please contact the publisher Elementary Physicochemical Processes on Solid Surfaces v P Zhdanov Institute of Catalysis Academy of Sciences of the USSR Siberian Branch Novosibirsk, USSR Springer Science+Business Media, LLC Free ebooks ==> www.Ebook777.com Library of Congress Cata log1ng-1n-PublicatIon Data Zhdanov, V P (ViadlnMr Petrovlch) [Elenentarnye flz1ko-kh1nMchesk1e protsessy na poverkhnost1 English] Elenentary physlcochenlcal processes on s o l i d surfaces / V P Zhadanov p en — (Fundamental and applied c a t a l y s i s ) Translation of: Eleientarnye f1z1ko-kh1n1chesk1e protsessy na poverkhnost1 Includes bibliographical references and Index ISBN 978-1-4899-2375-2 Solids—Surfaces Surfaces (Physics) Surface cheelstry I T i t l e II S e r i e s 0C173.4.S94Z4813 1991 530.4'27—dc20 91-29554 CIP ISBN 978-1-4899-2375-2 ISBN 978-1-4899-2373-8 (eBook) DOI 10.1007/978-1-4899-2373-8 © Springer Science+Business Media N e w York 1991 Originally published by Plenum Press, N e w York in 1991 Softcover reprint of the hardcover 1st edition 1991 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher www.Ebook777.com Preface to the Series Fundamental and Applied Catalysis Catalysis is important academically and industrially It plays an essential role in the manufacture of a wide range of products, from gasoline and plastics to fertilizers and herbicides, which would otherwise be unobtainable or prohibitively expensive There are few chemical- or oil-based material items in modem society that not depend in some way on a catalytic stage in their manufacture Apart from manufacturing processes, catalysis is finding other important and ever-increasing uses; for example, successful applications of catalysis in the control of pollution and its use in environmental control are certain to increase in the future The commercial importance of catalysis and the diverse intellectual challenges of catalytic phenomena have stimulated study by a broad spectrum of scientists including chemists, physicists, chemical engineers, and material scientists Increasing research activity over the years has brought deeper levels of understanding, and these have been associated with a continually growing amount of published material As recently as sixty years ago, Rideal and Taylor could still treat the subject comprehensively in a single volume, but by the 1950s Emmett required six volumes, and no conventional multivolume text could cover the whole of catalysis in any depth In- view of this situation, we felt there was a need for a collection of monographs, each one of which would deal at an advanced level with a selected topic, so as to build a catalysis reference library This is the aim of the present series, Fundamental and Applied Catalysis Some books in the series deal with particular techniques used in the study of catalysts and catalysis: these cover the scientific basis of the technique, details of its practical applications, and examples of its usefulness An v vi Preface industrial process or a class of catalysts forms the basis of other books, with information on: fundamental science of the topic, the use of the process or catalysts, and engineering aspects Single topics in catalysis are also treated in the series, with books giving the theory of the underlying science, and relating it to catalytic practice We believe that this approach is giving a collection of volumes that is of value to both academic and industrial workers The series editors welcome comments on the series and suggestions of topics for future volumes Billingham and Cardiff Martyn Twigg Michael Spencer Contents Introduction Chapter Vibrational Relaxation of Adsorbed Particles 1.1 General Approach to Describing Vibrational Relaxation 1.2 Phonon Mechanism of Relaxation 1.2.1 Relationship between the Simple Perturbation Theory and the Adiabatic Approximation 1.2.2 One-Mode Approximation 1.2.3 Relaxation Caused by Correlation Potential Proportional to Displacement of Adsorbed Particle from Equilibrium 1.2.4 Relaxation Caused by Correlation Potential Proportional to Displacement of Surface Atom from Equilibrium 1.2.5 Results and Discussion 1.3 Vibrational Relaxation via Interaction with Conduction Electrons 1.3.1 Dipole Approximation '.' 1.3.2 Hartree Fock Theory 1.3.3 Density Functional Scheme 1.3.4 Anderson Model 1.3.5 Population Relaxation due to Electron-Hole Pair Excitation 1.3.6 Pure-Phase Relaxation due to Elastic Scattering of Conduction Electrons vii 11 12 14 15 18 18 19 20 21 22 24 viii Contents 1.3.7 Pure-Phase Relaxation due to Electron-Hole Pair Scattering 1.3.8 Results and Discussion 1.4 Phenomenological Description of the Dynamics of Adsorbed Particles 1.4.1 Langevin Equation 1.4.2 Generalized Langevin Equation 1.4.3 Fokker-Planck Equation 1.5 Friction Coefficient 1.6 Experimental Data References 25 27 29 29 32 33 34 36 42 Chapter Dynamics of Molecular Processes on Surfaces 45 2.1 Transition State Theory 2.1.1 Partition Functions 2.1.2 Monomolecular Desorption 2.1.3 Associative Desorption 2.1.4 Bimolecular Reaction in the Adsorbed Layer; 45 48 49 51 the Langmuir-Hinshelwood Mechanism 51 2.1.5 Monomolecular Reactions in the Adsorbed Layer 2.1.6 Surface Diffusion 2.1.7 Monomolecular Adsorption 2.1.8 Dissociative Adsorption 2.1.9 Bimolecular Reaction: the Eley-Rideal Mechanism 2.1.10 Summary of Results 2.1.11 Some Experimental Results 2.2 Dynamical Calculations 2.2.1 Typical Experimental Results 2.2.2 Dynamics of Activated Adsorption 2.2.3 Dynamics of Activated Desorption 2.3 Nonequilibrium Effects 2.3.1 Rate Processes Limited by Coupling the Reaction Coordinate to the Bath 2.3.2 Desorption Stimulated by Adsorption 2.3.3 Using Energy of One Reaction to Accelerate Another Reaction 2.4 Nonadiabatic Effects 52 52 53 54 54 55 56 59 59 62 64 68 68 71 74 75 Free ebooks ==> www.Ebook777.com Contents ix 2.5 Dynamics of Surface Diffusion 2.5.1 Phenomenology 2.5.2 Energy Exchange between Adsorbed Particle and the Solid 2.5.3 Effect of the Potential Energy Surface Topology on Diffusion 2.5.4 Results of Some Estimations 2.5.5 Relaxation of the Lattice during Activated Jumps of Adsorbed Particle 2.5.6 Tunnel Diffusion 2.5.7 Some Experimental Data References 77 78 Chapter Statistics of Adsorbed Particles 99 3.1 Lattice-Gas Model, Lateral Interactions 3.2 General Statistical Relations 3.3 Approximate Statistical Methods 3.3.1 Mean-Field (Bragg-Williams) Approximation 3.3.2 Quasi-Chemical (Bethe-Peierls) Approximation 3.3.3 Transfer-Matrix Technique 3.3.4 Renonnalization-Group Method 3.3.5 Monte Carlo Simulations 3.4 Phase Diagrams of Adsorbed Particles 3.4.1 Notation of Surface Ordered Structures 3.4.2 Order Parameters 3.4.3 Universal Classes of Ordered Structures 3.4.4 Phase Diagrams 3.4.5 Critical Exponel].ts 3.5 Adsorbate-Induced Surface Reconstruction 3.5.1 First-Order Phase Transitions 3.5.2 Phenomenological Description of Continuous Phase Transitions 3.5.3 Order-Disorder Phase Transitions " 3.5.4 Displacive Phase Transitions References 99 102 103 103 108 111 113 115 116 117 118 118 118 126 128 129 www.Ebook777.com 78 82 86 92 92 94 95 133 137 138 141 300 Chapter problem was studied by Stiles and Metiu [72] employing also the Monte Carlo method The effect of limited mobility of adsorbed particles of one kind on thermal desorption spectra was discussed in [75] In real systems, this effect seems to be rather weak because usually the activation energy for diffusion is considerably lower than that for desorption If adsorption is accompanied by surface reconstruction, the rate processes in the adsorbed overlayer may be significantly affected by the limited mobility of metal atoms in the topmost surface layer (see, e.g., the data of [89] for the HlCu(llO) system) However, this problem has not been studied theoretically We have considered in this section some aspects of the kinetics of reactions limited by surface diffusion Finally, it should be noted that diffusion of adsorbed particles can play an important role in other processes on solid surfaces, e.g., in the ordering of chemisorbed overlayers (see Section 5.4) or in molecular beam epitaxy [76] The latter process has now become an extremely useful tool in the construction of well-ordered interfaces REFERENCES G Ehrlich and K Stolt, Annu Rev Phys Chem 31, 603 (1980) R Gomer, Vacuum 33, 537 ·(1983); Rep Prog Phys 53, 917 (1990) Surface Mobilities on Solid Materials, ed V T Binh (Plenum Press, New York, 1983) A G Naumovets and Yu S VeduJa, Surf Sci Rep 4, 365 (1985) Diflusion at Imer/aces, cds M Grunze, H J Kreuzer, and J J Weimer (Springer, Berlin, 1988); J D Doll and A F Voter, Annu Rev Phys Chem 38, 413 (1987); A Kapoor, R T Yang, and C Wong, Catal Rev Sci Eng 31, 129 (1989); G E Rhead, Int Math Rev 34, 261 (1989) G L Kellogg, J Chem Phys 83, 852 (1985); Surf Sci 187, 153 (1987); 192, L879 (1987) R C Jaldevic and L Elie, Phys Rev Lett 60, 120 (1988); T.-S Lin and Y.-W Chung, Surf Sci 207,539 (1989) J.-R Chen and R Gomer, Surf Sci 79,413 (1979) R DiFoggio and R Gomer, Phys Rev B 15, 3490 (1982); S C Wang and R Gomer, J Chem Phys 83, 4193 (1985) 10 R Morin, Surf Sci 155, 187 (1985) 11 M Tringides and R Gomer, J Chem Phys 84, 4049 (1986); D.-S Choi and R Gomer, Surf Sci 230, m (1990) Diffusion of Particles 301 12 L Boltzmann, Wiedemanns Ann 53, 959 (1894); C Matano, Jpn J Phys 8, 109 (1933) 13 R Butz and H Wagner, Sur[ Sci 63,448 (1977) 14 E Suliga and M Henzler, J Phys C 16, 1543 (1983) 15 Yu S Vedula, A T Luborets, and A G Naumovets, Zh Eksp Teor Fiz 77,773 (1979) (in Russian) [English translation: Sov Phys JEI'P SO, 397 (1980)) 16 A T Luborets, A G Naumovets, and Yu S Vedula, Sur[ Sci 120, 347 (19~2) 17 Yu S Vedula, A G Naumovets, and V V Poplavsky, Fiz Tverd Tela 30,2616 (1988) (in Russian) 18 Yu S Vedula, A G Naumovets, and V V Poplavsky, Ukr Fiz Zh 33, 934 (1988) (in Russian) 19 A G Naumovets, V V Poplavsky, and Yu S Vedula, Surf Sci 200, 321 (1988) 20 S M George, A M De Santolo, and R B Hall, Surf Sci 159, U25 (1985) 21 E G Seebauer and L D Schmidt, Chern Phys Lett 123, 129 (1986) 22 D A Mullins, B Roop, and J M White, Chern Phys Lett 129, 511 (1986) 23 J L Brand, A A Deckert, and S M George, Surf Sci 194,457 (1988); C H Mak, D A Deckert, and S M George, J Chern Phys 88, 5242 (1988) 24 E G Seebauer, A C F Kong, and L D Schmidt, J Chern Phys 88,6597 (1988) 25 D A Reed and G Ehrlich, Surf Sci 102, 588 (1981) 26 D A Reed and G Ehrlich, Surf Sci 105, 603 (1981) 27 V P Zhdanov, Surf Sci 149, L13 (1985) 28 V P Zhdanov, Surf Sci 177, L896 (1986) 29 V P Zhdanov, Surf Sci 194, (1988) 30 L Darken, Trans AIME 175, 184 (1948) 31 R Kubo, J Phys Soc Jpn 12, 570 (1957) 32 L D Landau and E M Lishitz, Statistical Physics (pergamon, Oxford, 1980) 33 M Bowker and D A King, Sur[ Sci 71, 583 (1978); 72, 208 (1978) 34 G E Murch and R J Thorn, Philos Mag A 40,477 (1979) 35 G E Murch, Philos Mag A 43, 871 (1981) 36 A A Chumak and A A Tarasenko, Surf Sci 91,694 (1980); Fiz Tverd Tela 22, 2939 (1980) (in Russian) 37 A A Tarasenko and A A Chumak, Poverkhnost' No.2, 35 (1983) (in Russian) 38 A A Tarasenko, Poverkhnost' No.5, 29 (1985) (in Russian) 39 A A Tarasenko and A A Chumak, Poverkhnost' No 11, 98 (1989) (in Russian) 40 H Asada and M Masuda, Surf Sci 99, U29 (1980) 41 H Asada, Surf Sci 166,271 (1986) 42 W Zwerger, Z Phys B 42, 333 (1981) 43 G Mazenko, J R Banavar, and R Gomer, Sur[ Sci 107, 459 (1981); E Oguz, O T Valls, G F Mazenko, J Luscombe, and S J Heiling, Sur[ Sci 118,572 (1982) 44 M A Gesley and L W Swanson, Surf Sci 159, 496 (1985) 45 E Oguz, Sur[ Sci 134, 777 (1983) 46 D R Bowman, Sur[ Sci 130, 348 (1983) 47 D R Bowman, R Gomer, K Muttalib, and M 1iingides, Sur[ Sci 138,581 (1984) 48 M 1iingides and R Gomer, Surf Sci ISS, 254 (1985) 49 M 1iingides and R Gomer, Surf Sci 145, 121 (1984) 50 M 1iingides and R Gomer, Surf Sci 166,440 (1986) 302 Chapter 51 A Sadiq and K Binder, Surf Sci 128, 350 (1983) 52 A Natori and H Ohtsubo, Surf Sci 171, 13 (1986); 184, 289 (1987) 53 X.-P Jang and H Metiu, J Chem Phys 88, 1891 (1988) 54 S M Paik and S Das Sanna, Chem Phys Lett 135, 128 (1987) 55 S M Paik and S Das Sanna, Surf Sci 208, L53 (1989) 56 V P Zhdanov, Phys Lett A 137,225 (1989) 57 V P Zhdanov, Phys Lett A 137,409(1989) 58 V P Zhdanov, Langmuir 5, 1044 (1989) 59 J W Haus and K W Kehr, Phys Rep 150, 264 (1987); S Havlin and D BenAvraham, Adv Phys 36,595 (1987); R Kirchheim and U Stolz, Acta Metall 35, 281 (1987); C H Male, H C Anderson, and S M George, J Chem Phys 88,4052 (1988); V Pereyra, G Zgrablich, and V P Zhdanov, Langmuir 6,691 (1990) 60 V OOsele and F A Huntley, Phys Lett ASS, 291 (1975) 61 V A Kaminsky and M G Slin'ko, Dokl Akod Nauk SSSR 238,377 (1978) (in Russian) 62 A A Ovchinnikov and S F Timashev, Dokl Akod Nauk SSSR 239, 643 (1978) (in Russian) 63 V A Kaminsky, B N Okunev, and A A Ovchinnikov, Dokl Akod Nauk SSSR 251, 636 (1980) (in Russian) 64 S Prager and H L Frisch, J Chem Phys 72, 2941 (1980) 65 D L Freeman and J D Doll, J Chem Phys 78,6002 (1983); 79, 2343 (1983); Surf Sci 134, 769 (1983) 66 R I Cukier, J Chem Phys 79, 2430 (1983); J Stat Phys 42, 69 (1986) 67 V P Zhdanov, Surf Sci 187, L642 (1987) 68 V P Zhdanov, Surf, Sci 195, L217 (1988) 69 S Sundaresan and K P Kaza, Surf, Sci 160, 103 (1985); Chem Eng Commun 35, (1985) 70 M Silverberg, A Ben-Shaul, and F Robenttost, J Chem Phys 83, 6501 (1985) 71 M Silverberg and A Ben-Shaul, J Chem Phys 87, 3178 (1987); Chem Phys Lett 134,491 (1987); J Stat Phys 52, 1179 (1988); Surf, Sci 214, 17 (1989) 72 M Stiles and H Metiu, Chem Phys Lett 128,337 (1986) 73 H S Carslaw and J C Jaeger, Conduction of Heat in Solids (Oxford University Press, Oxford, 1959), p 334 74 V Kuzovkov and E Kotomin, Rep Prog Phys 51, 1479 (1988) 75 A Sorda and I Karasova, Surf Sci 109,605 (1981); A Sorda, Surf, Sci 220,295 (1989); J W Evans and H Pale, Surf Sci 186, 550 (1987); 199, 28 (1988); J W Evans, D K Hoffman, and H Pale, Surf, Sci 192, 475 (1987) 76 R Kariotis and M G Lagally, Surf, Sci 216,557 (1989) 77 J Kjoll, T Ala-Nissila, and S C Ying, Surf Sci 218, L476 (1989) 78 A V Myshlyavtsev and G S Yablonskii, Poverkhnost' No 12, 36 (1990) (in Russian) 79 G Wahnsttom and V P Zhdanov, Surf Sci 247,74 (1991) 80 T.-S Lin, H.-J Lu, and R Gomer, Surf Sci 234, 251 (1990) 81 R Spitzl, H Nichas, B Poelsema, and G Cornsa, Surf Sci 239, 243 (1990) Conclusion To conclude this monograph on the theory of elementary rate processes on solid surfaces, we briefly fonnulate the main results and trace the possible vistas for further development We emphasize once again that the qualitatively new stage of experimental research on surface phenomena started quite recently, early in the 1970s, when much effort was devoted to studying adsorption on the surface of single crystals under high vacuum conditions by various physical methods (see Introduction) Theory responded to experimental achievements somewhat late The stream of theoretical investigations of surface phenomena grew sharply only late in the 1970s, as evidenced by the fact that the bulk of the references made in the present monograph are of theoretical works published after 1978 During the subsequent decade, the theory of phenomena occurring on solid surfaces, and, in particular, the rate theory of elementary physical and chemical processes with the participation of adsorbed particles have been significantly developed At present, the general approaches have been fonnulated for describing the dynamics of adsorbed particles during elementary acts of rate processes The main laws governing the mechanisms of vibrational relaxation of adsorbed particles have been clarified An estimation has been made of the typical range of relaxation rates corresponding to the different mechanisms of the energy exchange between adsorbed particles and the solid An analysis has been made of the role of vibrational relaxation in elementary processes on surfaces, in particular, of the possibility of realizing processes limited by relaxation as well as superequilibrium processes Nonadiabatic effects in elementary processes on the surface have been studied 303 304 Conclusion Detailed studies have· been made on the effect of lateral interactions between adsorbed particles on the various processes on the surface Phase diagrams of adsorbed overlayers as a function of the type of lattice and of lateral interactions have been classified A general approach has been developed for determining the rates of different processes (adsorption, desorption, elementary chemical reactions) on a uniform surface with lateral interactions taken into account Lateral interactions have been shown to influence the kinetics of different processes occurring under steady-state and transient (thermal desorption, titration) conditions Some experience has been gained of applying the general equations to describing the kinetics of real rate processes Detailed studies have been made of the dynamical and statistical aspects of surface diffusion The role of adsorbate diffusion in chemical reactions on a surface has been clarified The first models for such interesting phenomena as spontaneous and adsorbate-induced reconstruction of the surface have been introduced On the whole, dwing the recent decade our understanding of elementary processes on solid surfaces has been considerably enhanced At the same time, nearly all branches of the theory of rate processes on surfaces are, as a matter of fact, only at the first stage of development Almost everywhere, old concepts require refinement and new ones need to be created The general theory must be used much more widely to interpret phenomena in real systems Which of the problems dealt with in this monograph should attract the most attention? This question is not easy to answer In the author's opinion, of great interest, from the viewpoint of the general theory, is the study of adsorbate-induced surface reconstruction and of its effect on the kinetics of the processes occurring on the surface At present, investigations in this field are just beginning As the methods of quantum chemistry that provide evidence on the potential energy for the motion of nuclei are developed, the characteristics of the dynamics of adsorbed particles in the course of elementary acts of heterogeneous chemical reactions can be studied in more detail From the point of view of applications, it is of interest to use further the kinetic equations obtained within the framework of the lattice-gas model for describing the kinetics of particular surface processes Significantly more attention will be focused in the future on elementary processes on heterogeneous surfaces Index Accommodation coefficients, and sticking coefficients, 42 table of,41 Acetylene, adsorbed, notation for, 117 Activated, see also desorption adsorption, dynamics of, 62 complexes, immobile, 51 and lateral interactions, 270 272 number of, 49 translational freedom of, 46 Activation energy, see also Arrhenius parameters for associative desorption, 207 for atom self-diffusion, 94 for carbon monoxide oxidation, 237 effect of coverage on, 59 240 for desorption, 60 140 for diffusion, 56 95 265 for fonnic acid decomposition, 251 for hydrogen diffusion, 62 91 near neighbor effects, 149 for oxygen diffusion on tungsten, 263 284 and thermal desorption spectra, 239 Active sites, diffusion to, 295 Adiabatic approximation, and simple perturbation, 11 Adsorbate, induced changes, 179 209 lateral interaction effects, 152 notation for, 117 overlayer order-disorder phases, 107 Adsorbate (cont.) phonon coupling, 16 Adsorption, acetylene, notation for, 117 activated, dynamics of, 62 construction of isotherms, 131 desorption hysteresis, 132 of dinitrogen on iron, 61 dissociative, 54 154 171 heat of, 281 isothenns and chemical potentials, 153 kinetics, effects on 165 monomolecular, 151 167 of reactants, 191 particle trajectories, 79 precursor states, 166 preexponential factors for, 56 57 175 rate constant for, 155 rate and number of vacant sites, 192 stimulating desorption, 71 AES, Auger electron spectroscopy, Anderson model, 1821 36 Arrhenius parameters, see also activation energy; preexponential factors coverage, effects of, 173 for desorption, 173 180 precision of, 239 Associative desorption, 51 153 159 of hydrogen, 58 and lateral interactions, 157 preexponential factors for, 57 305 306 Associative desorption (cont.) and solid-state diffusion, 'lJJ7 Autocorrelation function, 260 262-5 Bardeen-Cooper-Scbrieffer superconductor, 139 Barium, diffusion on molybdenum, 265 Bethe-Peierls approximation, 108 110-1 150 159 160 284 Bimolecular reactions, preexponentials for, 57 Boltzmann-Matano method, 262 264 266 281285 Bosons,27 Bragg-Williams, mean-field approximation, 103 Carbon, reaction with oxygen, 66 Carbon dioxide, dissociative adsorption on nickel, 60 as excited product, 186 Carbon monoxide, adsorption, on copper, 28 infrared frequencies, 39 on iridium, 173 on nickel, 173 Ni-CO vibration, 16 30 40 on platinum, 40 preexponential factors for, 56 on rhodium, relaxation of, 37 on ruthenium, 173 sticking coefficient for, 170 desorption, from platinum, 201 of labelled, 74 preexponential factors for, 234 diffusion, activation parameters for, 56 on nickel, 262 on rhodium, 267 from surface carbon, 67 oxidation, 59 233 on copper, 212 on iridium, 233 Index Carbon monoxide (cont.) oxidation (cont.) oscillation of, 133 on palladium, 212 on platinum, 212 preexponential factors for, 234 rate of, 238 titration of oxygen, 234 Chain mechanism, for diffusion, 288 Charge density waves, 129 Chemical, diffusion, coefficient, 283 and particle mobility, 279 potential, and adsorption isotherm, 153 coverage dependence of, 112 and desorption rate, 150 Chemisorption, see also adsorption vibrational relaxation, 18 Compensation effects, 58 69 in carbon monoxide oxidation, 238 and coverage, 174 175 178 and data precision, 180 in diffusion, 291 prediction of, 179 and surface reconstruction, 179 Conduction electrons, 18 elastic scattering of, 24 Copper, carbon monoxide, adsorption on, 28 IR frequencies of, 39 oxidation of, 212 hydrogen dissociation on, 62 187 nitrous oxide dissociation on, 61 Correlation potential, and relaxation, 12 Coupling reactions, 68 74 Coverage, activation energy, effect on, 59 240 effect on phase diagram, 135 and chemical potential, 112 and compensation effect, 174 and desorption rate, 71274 and diffusion, 258 267 274 289 290 and island formation, 205 Index Coverage (cont.) during Langmuir-Hinshelwood reaction, 216 and sticking coefficient, 169 and thermal desorption spectra, 239 Critical, ordered 2-D system exponents, 127 temperature, 126 181 Cyclopropane isomerization, 61 70 Damping, surface motion, 90 Darkin equation, approximate nature of, 278280281 Debye, frequency, 36 89 model, 35 88 93 Desorption, activated, dynamics of, 64 effect on kinetics, 165 effect of lateral interactions, 157 effect of phase transition on, 184 activation parameters, 173 180 apparent, 140 for dinitrogen, 163 associative, 51 153 of hydrogen, 58 of carbon monoxide, from platinum, 201 preexponential factors, 234 hydrogen, from platinum, 209 from tungsten, 210 isothermal,212 laser induced, 94 lattice-gas model literature, 212 monomolecular, 49 147 167 neighbor effect on activation energy, 149 of nitrogen from nitric oxide, 246 oxygen, from palladium, 210 from silver, 209 from tungsten, 262 preexponential factors for, 234 preexponential factors for, 50 173 table, 60 307 Desorption (com.) rate, 159 179 and chemical potential, 150 and coverage, 71 and equilibrium constant, 72 maximum, 73 stimulated by desorption, 70-71 73-74 thermal spectra, 194 zero order, 199 Deuterium, accommodation coefficients for, 41 adsorbed on nickel, 187 diffusion on tungsten, 263 Diffusion, see also self-diffusion activation parameters for, 56 91 265 274 self-diffusion, 94 anisotropy of, 287 of barium on molybdenum, 265 of barium on tungsten, 265 of carbon monoxide, activation parameters, 56 on rhodium, 267 chain mechanism for, 288 coefficient, 78 chemical, 283 and coverage, 262 273 274 286 267 compensation effects in, 291 and coverage, 258 267 274 284 289 290 experimental data, 261 Fick's laws, 257 262 of hydrogen on nickel, 82 inhibition by adsorbates, 267 into solid, 206 in Langmuir layer, 271 of lanthanum on tungsten, 265 limiting surface reaction, 291 of lithium on metals, 265 of oxygen on tungsten, 263 particle, 29 257 mean-field approximation for, 271 mobility, 279 potential energy for, 274 of silver on germanium, 264 simulated, oxygen on tungsten, 283 Index 308 Diffusion (conI.) of sodium on tungsten, 262 264 surface, 52 77 observation of, 94 preexponential factors for, 57 and thermal desorption spectra, 205 to active sites, 295 tunnel effects in, 92 Dinitrogen, accommodation coefficients for, 41 adsorption, on iron, 61 on platinum, 28 on tungsten, 64 desorption, 74 activation energy, 163 from ruthenium, 246 split desorption peak, 246 on tungsten, sticking coefficient, 170 Dipole approximation, 18 Dissociation, energy for, 61 of hydrogen on lithium, 64 of nitric oxide on platinum, 162 Dissociative, adsorption, 54 154 171 dinitrogen on tungsten, 64 preexponential factors for, 57 Dynamics, of activated adsorption, 62 of activated desorption, 64 of adsorbed particles, 29 of surface diffusion, 77 Elastic scattering, of conduction electrons, 24 Electron, conduction, 24 Electron-hole pair, relaxation, 22 scattering, 25 Eley-Rideal mechanism, 54 66 156 adsorption preexponential factors, 57 Energy, see also activation energy; potential energy of adsorbed layer, 108 exchange with adsorbed particles, 78 EXAFS, extended X-ray absorption fine structure, Excited products, 184 186 Fano diagonalization, 21 Fermi golden rule, Fick's laws, 257 262 269 Field ion microscope, 94 261 Finite density of grains, theory of, 220 Fluctuation-dissipation theorem, 31 Foller-Planck equation, 33 68 78 81 Langevin equivalent, 33 Formic acid, decomposition mechanism, 250 decomposition on nickel, 194 249 Franck-Condon, approximation, 92 effects, 289 Friction, coefficient, 34 69 80 kernel,33 Germaaium, silver diffusion on, 264 Golden rule, 11 22 Harpooning, 75 Hartree, Hartree-Fock theory, 19 Hartree-Fock-Koopmans model, 20 Henon-Heiles model, 83 85 Hinshelwood, see LangmuirHinshelwood HREELS, high resolution electton ener;gy loss spectroscopy, Hydrogen, accommodation coefficients for, 41 associative desorption of, 58 desorption, from copper, 61 from platinum, 209 from tungsten, 210 diffusion, inhibition of, 267 on nickel, 82 84 dissociation, on copper, 62 Index Hydrogen (cont.) dissociation (cont.) on lithium, 64 on nickel, 63 reaction with oxygen, 241 242244 surface blocking by, 244 tunnel effects with, 92 Hydroxyl, hydrogen interaction with, 243 relaxation of, 37 Infrared, frequencies, adsorbed carbon monoxide, 39 spectroscopy, Ion core potential, screening of, 20 Iridium, carbon monoxide on, 173 174 234 diffusion of, 56 oxidation of, 233 241 oxygen titration, 238 desorption, of carbon dioxide, 234 of oxygen, 234 Iron, adsorption of dinitrogen on, 61 hydrogen phase diagram, 124 125 Ising model, 101 122 183 223 Islands, equations for, 204 formation of, 202 Isomerization, propylene from cyclopropane, 61 70 Isotherms, construction of, 131 isothermal desorption, 212 Isotopes, use of, 72 ISS, ion scattering spectroscopy, Jahn-Teller effect, 129 in restructuring, 137 Jump, length, 79 81 267 275 rate equation for, 279 Kassel model, 69 309 Kinetics, in adsorbed layers, 47 of carbon monoxide oxidation, 240 of catalytic reactions, 145231 equations for activated species, 165 general comments, 231 of jumping, 279 limited by diffusion, 291 mobility effects on, 35 299 modelling nonidea1 behavior, 146 of monomolecular adsorption, 151 non-steady state, 291 nonexponential forms, 295 of phase transitions, 214 precursor states, effects on, 165 pressure effects on, 245 steady state, 191,295 surface reaction equations, 35 147 191 and transition state theory, 45 Kinks, and their motion, 226 Kolmogorov entropy, 86 Kubo equations, 280 286 Landau, Landau-Ginzburg equation, 222 Landau-Zener model, 76 mean-field equivalent, 134 theory, 179 290 Langevin equation, 29 Fokker-Planck equivalent, 33 general form, 32 64 67 78 Langmuir, Langmuir layer, diffusion in, 271 Langmuir-Hinshelwood mechanism, 51 59 156 196202213 291 299 carbon monoxide oxidation, 59 233 241 coverage effects, 216 241 and thermal desorption spectra, 205 Lanthanum, diffusion on tungsten, 265 Laser, induced thermal desorption, 94 265 picosecond pulses, 36 Lateral interactions, 164 184 197 213 233267 310 Lateral interactions (cont.) and activated complex, 270 272 between CO-CO and 0-0, 236 and coverage, 247 in desorption, 157 160 175 184 208 213 in formic acid decomposition, 251 and island formation, 204 in nitric oxide decomposition, 246 with precursor states, 167 and reaction rate, 158 and split thermal desorption peaks, 208 Lattice, energy transfer to, 68 78 lattice-gas model, 99 111 212 lattice-gas model literature, 212 lattice-gas/lattice-liquid, phase transition, 104 relaxation of, 92 shapes of, 81 LEED, low energy electron diffraction, 2216219 of carbon monoxide on nickel, 40 hydrogen surface reconstruction, 136 hydrogen on tunsgen, 133 135 intensity and phase change, 124 Lifshits-Slyozov theory, 219 correction to, 221 Linewidth, carbon monoxide on metals, 39 carbon monoxide on Pt(lll), 41 fluctuation-dissipation theorem, 31 Liouville equation, LITD, laser induced thermal desorption, 94 Lithium, diffusion on metals, 265 284 diffusion on tungsten, 284 hydrogen dissociation on, 64 London-Eyring-Polanyi-Sato potential, 63 Lyapunov exponent, 86 Markov approximation, 32 Mass action, law of, 47 Index Mean-field approximation, bilayer desorption, 162 164 for desorption, 181 for diffusion, 272 Landau theory equivalent, 134 for particle diffusion, 271 Methane, dissociation on tungsten, 61 Mica, isomerization catalyst, 61 Mobility, effect on reaction kinetics, 299 drift in external field, 283 of oxygen atoms at low temperature, 249 Molecular, adsorption preexponeiltial factors, 57 desorption preexponential factors, table, 57 Molybdenum, diffusion of barium on, 265 Monomolecular, adsorption and desorption, 167 adsorption of reactants, 191 reactions, preexponentials for, table, 57 surface reactions, 52 Monte Carlo simulations, 115 162 199 202 213 215 223 247 281 283 285 288299 Morse potentials, 12 17 Nearest-neighbor interactions, see lateral interactions Nernst-Einstein relation, 279 Nickel, carbon monoxide, diffusion on, 56 262 carbon monoxide on, 173 176 178 262 deuterium on, 187 dissociation, of carbon dioxide on, 60 of formic acid on, 194 249 of hydrogen on, 63 hydrogen, diffusion on, 82 phase diagram for, 124 Index Nickel (cont.) Ni-CO stretch vibration, 16 30 39 40 oxygen, phase diagram for, 124 vibration of particles on, 15 Nitric oxide, adsorbed on platinum, 37 173 decomposition, 245 lateral interactions during, 246 on platinum, 162299 on rhodium, 209 Nitride surface, desorption from, 74 Nitrogen, see dinitrogen Nitrous oxide, dissociation on copper, 61 Nonadiabatic effects, 75 Nucleation, in phase transition, 215 One-mode approximation, 11 Order parameters, effect of coverage on, 136 Oscillation, of adsorbed particles, 92 particle oscillation between cells, 84 reactions, model for, 133 Overlayer, order-disorder in, 107 Oxidation, of carbon monoxide, on copper, 212 on iridium, 233 on palladium, 212 preexponential factors for, 234 of surface carbon, 66 Oxygen, adsorbed on nickel, 17 desorption, from palladium, 210 from ruthenium, 209 from silver, 209 from tungsten, 262 preexponential factors, 234 diffusion on tungsten, activation parameters for, 263 with hydrogen on platinum, 241 mechanism of water formation, 242 simulated diffusion on tungsten, 283 311 Oxygen (cont.) surface mobility at low temperature, 249 titration by carbon monoxide, 234 on tungsten, 282 Palladium, carbon monoxide on, 39 hydrogen on, 187 oxidation of carbon monoxide on, 212 241 oxygen desorption from, 210 Particles, diffusion of, 29 257 equations for, 267 mean-field approximation for, 271 mobility of, and chemical diffusion, 279 and friction, 35 oscillations of, 92 between cells, 84 potential energy of, 108 self-diffusion of, 275 statistical relations for, 102 vibrational relaxation measurements of,36 Partition functions, for adsorbed molecules, 48 Peierls, see also Bethe-Peierls approximation, instability, 138 179 Perturbation theory, Phase, phase diagrams, of adsorbed particles, 116 118 coordinates for, 121 coverage effect on, 135 and critical temperature, 126 for hydrogen on palladium, 123 overlayer order-disorder, 107 180 sodium on ruthenium, 128 phase transition, effect on desorption, 184 diagrams, table of, 120 in formic acid decomposition, 251 kinetics of, 214 312 Phase (cont.) phase transition (cont.) lattice-gas/lattice-liquid, 104 121 nucleation in, 215 surface gas-surface liquid, 194 and symmetry relations, 118 Phonon-adsorbate coupling, 16 Platinum, carbon monoxide, adsorbed on, 40 oxidation on, 212 241 dinitrogen adsorbed on, 28 dissociation of nitric oxide on, 162 hydrogen, desorption from, 209 reaction with oxygen on, 241 nitric oxide on, 37, 173299 notation for acetylene on, 117 vibration of particles on, 15 Polyatomic molecules, vibrational exchange in, 18 Potential, barrier in transition state theory, 49 energy, for diffusion, 274 of particles, 108 surface topology, 82 Precursor, layer, 165 states, 166 Preexponential factors, see also Arrhenius parameters for adsorption, 175 for carbon monoxide oxidation, 234 effect of coverage on, 58 59 for desorption, 50 60 173247 measurement of, 56 for oxygen, desorption, 234 diffusion on tungsten, 263 for surface reactions, 46 53 55 57 158 234 Pressure-gap, 232 245 Rate, of adsorption, 155 Index Rate (cont.) of carbon monoxide oxidation, 240 of desorption, 159 179 diffusion and coverage effects, 298 theory of surface reactions, 145 191 Reconstruction, via adsorbate, 128 290 of tungsten by hydrogen, 136 Redhead's equations, 195 207 Relaxation, of carbon monoxide on rhodium, 37 and conduction electrons, 18 and correlation potential, 12 and electron-hole pairs, 22 of lattice, 92 measurement of, 36 phonon mechanism, of silica hydroxyl, 37 vibrational, Renormalization-group method, 113 Rhodium, carbon monoxide, desorption from, 74 diffusion on, 267 oxidation on, 241 relaxation on, 37 nitric oxide, decomposition on, 209 self diffusion of, 89 Rideal, see Eley-Rideal Ruthenium, adsorbed sodium, phase diagram, 128 carbon monoxide on, 173 174 176 diffusion of, 56 desorption, of dinitrogen, 246 of oxygen, 209 Self-diffusion, on metal surfaces, 88 288 of particles, 275 Silica, hydroxyl relaxation on, 37 Silver, diffusion on germanium, 264 oxygen desorption from, 209 SIMS, secondary ion mass spectroscopy, Index Smoluchowski equation, 34 Sodium, diffusion on tungsten, 262 264 on ruthenium phase diagram, 128 Solid, diffusion into 206 solid-state diffusion, and IDS, 205 Steady-state, kinetics, 191 295 Sticking coefficient, and accommodation coefficients, 42 for carbon monoxide on nickel, 170 definition of, 168 and desorption order, 199 experimental values of, 58 for nitrogen on tungsten, 170 precursor state effects on, 166 relative values of, 177 Stimulated desorption, 70-1 73-4 Strip method, 264 266 Sulfur, adsorbed on nickel, 17 contamination, effect on desorption, 61 Super lattice, 217 Superconductors, 139 Surface, adsorbate induced changes, 209 atoms, vibration of 11 blocking by hydrogen, 244 carbon monoxide, diffusion of, 56 damping motion on, 90 diffusion, activation parameters for, 95 dynamics of, 77 limited reactions, 291 observation of, 94 elementary cells on, 48 53 hydrogen diffusion on copper, 62 mobility of oxygen 249 potential energy of, 82 reactions, carbon monoxide oxidation 133 212 233-4 238 effect of coverage on, 240 kinetic equations for, 35 45-7 145-7 191231240 313 Surface (cont.) reactions (cont.) preexponential factors for, 46 53-7 158234 rate theory of 145 reconstruction, and compensation effects, 179 via adsorbate, 128 179 290 restructuring, during thermal desorption, 209 science techniques, structure notations, 117 top layer, 80 IDS, thermal desorption spectroscopy, Temperature, effect on linewidth, 41 Thermal desorption, laser induced, 265 lateral interactions and split peaks, 208 spectra, 173 194 activation energies from, 239 calculated, 198 237 experimental and calculated compared, 239 248 for Langmuir-Hinshelwood mechanism, 205 model for, 133 peak positions in, 195 Redhead's equations, 195 solid-state diffusion effects, 205 split nitrogen peak, 246 surface restructuring during, 209 Titration, of carbon monoxide by oxygen, 234 Trajectories, of surface particles, 79 85 Transfer-Matrix technique, 111 Transition, metals for nitric oxide decomposition, 245 state theory, 45 for desorption, 149 for monomolecular adsorption, 151 potential barrier top, 49 Transport coefficients, 274 Triangular diagrams, 252 Free ebooks ==> www.Ebook777.com 314 Index Tungsten, desorption, of hydrogen from, 210 of oxygen from, 262 diffusion, of barium on, 265 of deuterium on, 263 of lanthanum on, 265 of oxygen on, 263 self-diffusion,89 simulated oxygen on, 283 of sodium on, 264 dissociation, of dinitrogen on, 64 of methane on, 61 oxygen, adSOJbed on, 282 phase diagram for, 124 sticking coefficient of dinitrogen on, 172 Tunnel effects, in diffusion, 92 267 270 289 Universality classes, 119 UPS, ultraviolet photoelectron spectroscopy, Van der Waals interactions, 100 Vibration, excited products, 184 relaxation, measurement of, 36 on metals, 15-6 of surface hydroxyl, 37 via conduction electrons, 27 Water, mechanism of formation, 242 Williams, see Bragg-Williams approximation Work function, 265 XPS, X-ray photoelectron spectroscopy, www.Ebook777.com ... volume immediately upon publication Volumes are billed only upon actual shipment For further information please contact the publisher Elementary Physicochemical Processes on Solid Surfaces v P Zhdanov... VIBRATIONAL RELAXATION VIA INTERACTION WITH CONDUCTION ELECTRONS Vibrational relaxation due to interaction with conduction electrons is significant in the case of high-frequency vibrations of particles... excitation of phonons and electron-hole pairs (Chapter 1) and the dynamics of more complex processes such as adsorption, desorption, elementary chemical reactions, and surface diffusion (Chapter