(Ebook) Oxide Surfaces by D.P. Woodruff (Eds.

) ISBN
9780444507457, 0444507450 Pdf Download

https://ebooknice.com/product/oxide-surfaces-2143162

★★★★★
4.7 out of 5.0 (84 reviews )

DOWNLOAD PDF

ebooknice.com
 (Ebook) Oxide Surfaces by D.P. Woodruff (Eds.) ISBN
9780444507457, 0444507450 Pdf Download

EBOOK

Available Formats

■ PDF eBook Study Guide Ebook

EXCLUSIVE 2025 EDUCATIONAL COLLECTION - LIMITED TIME

INSTANT DOWNLOAD VIEW LIBRARY

 We believe these products will be a great fit for you. Click
the link to download now, or visit ebooknice.com
to discover even more!

(Ebook) Surface Alloys and Alloys Surfaces by D.P. Woodruff

(Eds.) ISBN 9780444511522, 0444511520

https://ebooknice.com/product/surface-alloys-and-alloys-surfaces-1188972

(Ebook) Vagabond, Vol. 29 (29) by Inoue, Takehiko ISBN

9781421531489, 1421531488

https://ebooknice.com/product/vagabond-vol-29-29-37511002

(Ebook) Oxide Surfaces by James A. Wingrave ISBN 9780824700003,

9781420030280, 0824700007, 1420030280

https://ebooknice.com/product/oxide-surfaces-4767416

(Ebook) Boeing B-29 Superfortress ISBN 9780764302725, 0764302728

https://ebooknice.com/product/boeing-b-29-superfortress-1573658
(Ebook) Jahrbuch für Geschichte: Band 29 ISBN 9783112622223,
3112622227

https://ebooknice.com/product/jahrbuch-fur-geschichte-band-29-50958290

(Ebook) Harrow County 29 by Cullen Bunn, Tyler Crook

https://ebooknice.com/product/harrow-county-29-53599548

(Ebook) 29, Single and Nigerian by Naijasinglegirl ISBN

9781310004216, 1310004218

https://ebooknice.com/product/29-single-and-nigerian-53599780

(Ebook) Organometallic Chemistry, Volume 29 by M. Green ISBN

0854043284

https://ebooknice.com/product/organometallic-chemistry-volume-29-2440106

(Ebook) Communication Yearbook 29 by Pamela J. Kalbfleisch (ed.)

ISBN 9780805855814, 0805855815

https://ebooknice.com/product/communication-yearbook-29-5293350
THE CHEMICAL PHYSICS OF SOLID SURFACES
 THE CHEMICAL PHYSICS OF SOLID SURFACES

Volume 1
CLEAN SOLID SURFACES

Volume 2
ADSORPTION AT SOLID SURFACES

Volume 3
CHEMISORPTION SYSTEMS

Volume 4
FUNDAMENTAL STUDIES OF HETEROGENEOUS CATALYSIS

Volume 5
SURFACE PROPERTIES OF ELECTRONIC MATERIALS

Volume 6
COADSORPTION, PROMOTERS AND POISONS

Volume 7
PHASE TRANSITIONS AND ADSORBATE
RESTRUCTURING AT METAL SURFACES

Volume 8
GROWTH AND PROPERTIES OF ULTRATHIN EPITAXIAL LAYERS

Volume 9
OXIDE SURFACES
 THE CHEMICAL PHYSICS
OF SOLID SURFACES

EDITED BY

D.P.WOODRUFF

B.Sc. (Bristol), Ph.D., D.Sc. (Warwick)

Professor of Physics,
University of Warwick

VOLUME 9

OXIDE SURFACES

2001
ELSEVIER
AMSTERDAM - LONDON - NEW YORK - OXFORD - PARIS - SHANNON - TOKYO
ELSEVIER SCIENCE B.V.
Sara Burgerhartstraat 25
RO. Box 211, 1000 AE Amsterdam, The Netherlands

© 2001 Elsevier Science B.V. All rights reserved

This work is protected under copyright by Elsevier Science, and the following terms and conditions apply to its use:

Photocopying
Single photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission
of the Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying,
copying for advertising or promotional purposes, resale, and all forms of document delivery. Special rates are available
for educational institutions that wish to make photocopies for non-profit educational classroom use.

Permissions may be sought directly from Elsevier Science Global Rights Department, PO Box 800, Oxford 0X5 1DX, UK; phone:
(+44) 1865 843830, fax: (+44) 1865 853333, e-mail: [email protected]. You may also contact Global Rights directly
through Elsevier's home page (http://www.elsevier.nl), by selecting 'Obtaining Permissions.

In the USA, users may clear permissions and make payments through the Copyright Clearance Center, Inc., 222
Rosewood Drive, Danvers, MA 01923, USA; phone: (+1) (978) 7508400, fax: (+1) (978) 7504744, and in the UK through
the Copyright Licensing Agency Rapid Clearance Service (CLARCS), 90 Tottenham Court Road, London W1P OLR UK;
phone: (+44) 207 631 5555; fax: (+44) 207 631 5500. Other countries may have a local reprographic rights agency for
payments.

Derivative Works
Tables of contents may be reproduced for internal circulation, but permission of Elsevier Science is required for external
resale or distribution of such material. Permission of the Publisher is required for all other derivative works, including
compilations and translations.

Electronic Storage or Usage

Permission of the Publisher is required to store or use electronically any material contained in this work, including any
chapter or part of a chapter.

Except as outlined above, no part of this work may be reproduced, stored in a retrieval system or transmitted in any form
or by any means, electronic, mechanical, photocopying, recording or otherwise, without prior written permission of the
Publisher. Address permissions requests to: Elsevier Science Global Rights Department, at the mail, fax and e-mail
addresses noted above.

Notice
No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of prod-
ucts liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas con-
tained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification
of diagnoses and drug dosages should be made.

ISBN 0-444-50745-0 (Vol. 9)

ISBN 0-444-41971-3 (Series)

First edition 2001

Library of Congress Cataloging in Publication Data

A catalog record from the Library of Congress has been applied for.

© T h e paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper).
Printed in The Netherlands.
Contributors to Volume 9

A. BARBIER CEA-Grenoble,
Departement de Recherche Fondamentale sur la Matiere
Condensee,
SP2M,
17, rue des Martyrs,
38054 Grenoble Cedex, France

M.A. BARTEAU Center for Catal3l;ic Science and Technology,

Department of Chemical Engineering,
University of Delaware,
Newark,
DE 19716, USA

S.A. CHAMBERS Environmental Molecular Sciences Laboratory,

Pacific Northwest National Laboratory,
PO Box 999, MS K8-93
Richland,
WA 99352, USA

C.C. CHUSUEI Department of Chemistry,

P.O. Box 30012,
Texas A&M University,
College Station,
TX 77842-3012, USA

B.G. DANIELS Surface Science Research Centre and Chemistry Department,

Manchester University,
Manchester M l 3 9PL, United Kingdom

U. DIEBOLD Department of Physics,

Tulane University,
New Orleans,
LA 70118, USA
R.G. EGDELL Inorganic Chemistry Laboratory,
University of Oxford
South Parks Road,
Oxford 0X1 3QR, United Kingdom

H.-J. FREUND Fritz-Haber-Institut der Max-Planck-Gesellschaft,

Department of Chemical Physics,
Faradayweg 4-6,
14195 Beriin, Germany

D.W. GOODMAN Department of Chemistry,

P.O. Box 30012,
Texas A&M University,
College Station,
TX 77842-3012, USA

B.E. HAYDEN Department of Chemistry,

University of Southampton,
Highfield,
Southampton SO 17 IB J, United Kingdom

V.E. HENRICH Department of Applied Physics,

Yale University,
P.O.Box 208284,
New Haven,
CT 06520, USA

K. HERMANN Fritz-Haber-Institut der Max-Planck-Gesellschaft,

Faradayweg 4-6,
14195 Berlin, Germany

H. KUHLENBECK Fritz-Haber-Institut der Max-Planck-Gesellschaft,

Department of Chemical Physics,
Faradayweg 4-6,
14195 Berlin, Germany
R. LINDSAY Surface Science Research Centre and Chemistry Department,
Manchester University,
Manchester Ml3 9PL, United Kingdom

D.C. MEIER Department of Chemistry,

P.O. Box 30012,
Texas A&M University,
College Station,
TX 77842-3012, USA

C. NOGUERA Laboratoire de Physique des Solides,

UMR CNRS 8502,
Universite Paris-Sud,
91405 Orsay, France

G. PACCHIONI Dipartimento di Scienza dei Materiali,

Universita di Milano-Bicocca,
Istituto Nazionale per la Fisica della Materia,
via Cozzi, 53,
20125 Milano, Italy

G. RENAUD CEA-Grenoble,
Departement de Recherche Fondamentale sur la Matiere
Condensee,
SP2M,
17, rue des Martyrs,
38054 Grenoble Cedex, France

T. RISSE Fritz-Haber-Institut der Max-Planck-Gesellschaft,

Department of Chemical Physics,
Faradayweg 4-6,
14195 Berlin, Germany

G.S. ROHRER Department of Materials Science and Engineering,

Carnegie Mellon University,
Pittsburgh,
PA 15213-3890, USA
J.L. DE SEGOVIA Institute de Ciencia de Materiales de Madrid,
CSIC
E-28049 Cantoblanco Madrid, Spain

A.B. SHERRILL Center for Catalytic Science and Technology,

Department of Chemical Engineering,
University of Delaware,
Newark,
DE 19716, USA

G. THORNTON Surface Science Research Centre and Chemistry Department,

Manchester University,
Manchester Ml3 9PL, United Kingdom

E.M. WILLIAMS Surface Science Research Centre,

The University of Liverpool,
Liverpool L69 3BX, United Kingdom

M.WITKO Institute of Catalysis and Surface Chemistry,

Polish Academy of Sciences,
ul. Niezapominajek,
30239 Cracaw, Poland
Preface
During the late 1960s and 1970s the commercial availability of ultra-high
vacuum (UHV) systems allowed the development of a plethora of new
techniques which were devised to probe materials in a surface-specific fashion,
and this in turn led to the creation of modem surface science; the study of the
structural, electronic and chemical properties of extremely well-characterised
surfaces on an atomic scale. When David King and I first conceived this series
of volumes in the later 1970s our objective was to recognise the growing
maturity of this new scientific discipline which was already starting to apply
these techniques in a combined fashion to understand surface processes. In the
20 years since the first volume was published, this perception has certainly
proved to be well-founded, and while new techniques have continued to
appear, they have rapidly been assimilated into the general armoury of
methods (the increasing pervasiveness of scanning probe microscopies is very
evident in the current volume), and it is the combination of methods which has
proved most effective.
The topic of the present volume, Oxide Surfaces, has been in many ways a
'Cinderella' of surface science; while the importance of oxide surfaces has
been long recognised, the perceived difficulty of preparing and probing oxide
surfaces (especially insulating oxide surfaces) meant that there was far more
attention devoted in the mainstream of the subject to metal and semiconductor
surfaces. There were notable exceptions, and some of the authors contributing
to this volume have made major contributions to the topic throughout the
whole period of development of modem surface science. The study of oxide
surfaces has been a major growth area in the last few years, partly encouraged
by new methods including the use of epitaxial oxide films grown on metallic
substrates. These films are more amenable to study by electron spectroscopies,
but raise new issues of surface characterisation and associated properties.
This volume provides a view of some of the main areas of development and
of recent progress in the study of well-characterised oxide surfaces. The first
chapter by Henrich, one of the pioneers of modem surface studies of oxides,
and co-author of the first text on the subject, provides an overview of the
subject and relates the remaining chapters to this overview. Chapters 2 to 4, by
Noguera, by Pacchioni and by Hermann and Witko, are concemed with the
theory of oxides surfaces; they cover a range of materialsfi*omsimple rocksalt
stmctures such as MgO through to the complexity of transition metal oxides,
and also present some complementary methods of modelling and calculation.
These theoretical studies also address the key issue of surface defects, and
cover some aspects of adsorption at oxide surfaces. In some ways oxide
surfaces is a topic in which theory was, for some years, ahead of experiment,
and hence unchallenged. This was especially tme in the predictions and
measurements of surface structure, but substantial experimental advances have
been made in the last few years in quantitative structure determination of oxide
surfaces and this progress is surveyed in Chapters 5 and 6; Renaud and
Barbier focus on the achievements of surface X-ray scattering methods (an
approach which circumvents one of the main problems of surface charging
when using electron probes), while Lindsay, Daniels and Thornton concentrate
on other methods, and especially on adsorbate structure determination. A
closely related issue is the structural characterisation of thin epitaxial oxide
films, and this is described in Chapter 7 by Chambers. Crucial complementary
structural information on oxide surfaces structures, especially of Ti02, has
been provided in the last few years by scanning probe microscopies, and this is
the focus of Diebold's Chapter 11. Because of the important role played by
surface stoichiometry of oxides in both structure and reactivity, this work also
relates quite closely to the content of Chapters 8 (Freund, Kuhlenbeck and
Risse), 9 (Chusuei, Meier and Goodman), 10 (Sherrill and Barteau) and 12
(Rohrer) which all address different aspects of the chemistry and reactivity
(including photochemistry) of oxide surfaces (including those of thin films), an
area which constitutes one of the primary motivations for the study of oxide
surfaces. Chapters 13 (Hayden) and 14 (Egdell) discuss two general aspects of
oxide surfaces, their vibrational and electronic properties; while the titles
suggest an emphasis on physical properties, vibrational spectroscopies, in
particular, are also an important probe of adsorbate interactions and are
especially relevant to chemical properties. The final chapter by de Segovia and
Williams describes another topic of especial relevance to oxide surfaces and
closely related to their photochemistry, that of DIET (desorption induced by
electronic transitions).

January 2001 D.P.Woodruff

Contents
Preface ix

Chapter 1 (V.E. Henrich)

Metal oxide surfaces and interfaces: concepts and issues 1

1. Introduction 1
2. Interesting bulk properties 2
2.1 Electronic properties 2
2.2 Crystal structure 8
3. From bulk to surface 9
4. Electrons on oxide surfaces 16
5. Oxide-gas, -liquid and -solid interfaces 21
6. Adsorption on metal oxides 25
7. Endnote 31
Acknowledgements 33
References 33

Chapter 2 (C. Noguera)

Clean oxide surfaces: a theoretical review 35

1. Introduction 35
2. Numerical methods 36
2.1 Classical approaches 36
2.2 Semi-empirical quantum methods 37
2.3 The ab initio HF method and methods beyond 38
2.4 The ab initio Density Functional Theory and methods beyond 39
2.4.1 The Self-Interaction Correction (SIC) method 40
2.4.2 The GW method 41
2.4.3 The LDA+U method 42
2.5 General features for simulating surfaces 43
3. Review of literature 44
3.1 Fluorite MO2 and anti-fluorite M2O structures 45
3.2 Rocksalt structure 45
3.3 Corundum structure 49
3.4 Rutile structure 51
3.5 Wurtzite structure 53
3.6 Perovskite structure 54
3.7 Other oxides 57
4. Discussion of non-polar stoichiometric surfaces 59
4.1 Atomic structure 59
4.2 Energetics 61
4.3 Electron distribution 62
4.4 One particle excitations 65
4.5 Two particle excitations 68
5. Non-stoichiometric surfaces 69
5.1 Atomic relaxation 70
5.2 Charge and spin distribution 70
 5.3 Spectroscopic signature 72
5.4 Energetics 73
6. Polar surfaces 75
6.1 Criterion for surface polarity 76
6.2 Models of electronic structure in iono-covalent materials: application to 78
polar surfaces
6.3 Surface processes relevant for polarity healing 80
6.4 Summary 83
7. Conclusion 85
References 86

Chapter 3 (G. Pacchioni)

Theory of point defects at the MgO surface

1. Introduction 94
2. Quantum chemical description of ionic crystals 95
2.1 Cluster models 96
2.2 Embedding schemes 98
2.3 Solutions of the Schrodinger equation 99
3. Role and nature of defects at the MgO surface 101
3.1 Low-coordinated cations 103
3.2 Low-coordinated anions 107
3.3 Hydroxyl groups 109
3.4 Anion vacancies 110
3.4.1 Charge distribution 111
3.4.2 Hyperfme interactions 113
3.4.3 Stability and formation energies 115
3.4.4 Energy levels and ionisation potentials 116
3.4.5 Barriers to vacancies diffusion 117
3.4.6 Optical spectra 118
3.4.7 Chemical reactivity 120
3.5 Cation vacancies 121
3.6 Divacancies 122
3.7 Impurity atoms 124
3.80" radical anions 126
3.9(lll)microfacets 128
4. Conclusions 129
Acknowledgements 129
References 130

Chapter 4 (K. Hermann and M. Witko)

Theory of physical and chemical behaviour of transition metal oxides: vanadium

and molybdenum oxides
1. Introduction 136
2. Vanadium oxides 139
2.1 Vanadium oxide bulk systems 140
2.1.1 Geometric structure 140
2.1.2 Electronic properties 142
 2.2 Vanadium oxide surfaces 148
2.2.1 Geometric structure 148
2.2.2 Physical and chemical properties 152
(a) Properties of clean surfaces 152
(b) Surface oxygen vacancies 157
(c) Adsorption 162
3. Molybdenum oxides 168
3.1 Molybdenum oxide bulk systems 170
3.1.1 Geometric structure 170
3.1.2 Electronic structure 172
3.2 Molybdenum oxide surfaces 172
3.2.1 Geometric structure 172
3.2.2 Physical and chemical properties 175
(a) Properties of clean surfaces 175
(b) Surface oxygen vacancies 182
(c) Adsorption 186
Synopsis 190
Acknowledgement 191
References 191

Chapter 5 (R. Lindsay, B.G. Daniels and G. Thornton)

Geometry of adsorbates on metal oxide surfaces

1. Introduction 199
2. Magnesium oxide - MgO 202
2.1MgO(100)-H2O 202
2.2MgO(100)-C2H2 206
2.3MgO(100)-CO 207
2.4MgO(100)-CO2 208
2.5MgO(100)-Ca 209
2.6MgO(100)-Ag 210
2.7MgO(100)-Pd 212
2.8MgO(100)-Ni 212
2.9MgO(100)-Fe 213
3. Nickel oxide-NiO 213
3.1NiO(100)-NO 214
3.2NiO(100)-CO 216
3.3NiO(100)-H2S 217
3.4NiO(lll)-NO 218
3.5NiO(lll)-CO 219
4. Titanium dioxide - Ti02 219
4.1TiO2(110)-HCOOH 221
4.2 Ti02(l 10) - H3CCOOH 223
4.3 Ti02(l 10) - H5C2COOH 224
4.4 Ti02(l 10) - H5C6COOH 224
4.5 Ti02(l 10) - bi-isonicotinic acid 225
4.6TiO2(110)-Na 226
4.7 Ti02(l 10) - Na/C02 227
4.8 Ti02(l 10) - (NH4)6Mo7024.4H20 228
 4.9 Ti02(l 10) - {Rh(CO)2Cl}2 230
4.10TiO2(110)-SO2 231
4.11TiO2(110)-K 232
5. Aluminium oxide - AI2O3 233
5.1a-Al2O3(0001)-Cu 233
5.2 y-like AbOsCOOO 1) - di-tert-butyl nitroxide 234
6. Chromium oxide - Cr203 235
6.1Cr2O3(0001)-CO2 235
6.2Cr2O3(0001)-NO 236
7. Iron oxide - FexOy 236
7.1 FeO(lll)-H5C6CHCH2 237
7.2 Fe304(l 11) - H5C6CHCH2 237
8. Zinc oxide-ZnO 238
8.1 ZnO(loiO) - HCOOH 238
8.2ZnO(10i0)-CO2 ^^^
8.3ZnO(10i0)-C6H6 ^^^
8.4ZnO(10i0)-C5H5N 240
8.5 ZnO (lOiO) - C6N3H5,C7N2H6, C7N2H6, C7N3H7 241
8.6ZnO(000i)-CO 242
8.7ZnO(000i)-CO2 243
8.8 ZnO (OOOi) - HCOOH 243
8.9ZnO(000i)-C5H5N 244
8.10 ZnO (OOOi)-K 244
8.11ZnO(0001)-CO 246
8.12ZnO(0001)-CO2 246
8.13 ZnO(OOOl) - HCOOH 247
8.14 ZnO(OOOl) - CH3OH 247
8.15ZnO(0001)-C6H6 247
8.16 ZnO(OOOl) - CeHsOH 248
8.17 ZnO(OOOl) - C5H5N 248
9. Copper (I) oxide - CU2O 249
9.1 C u 2 0 ( l l l ) - C H 3 0 H 249
Acknowledgements 249
References 250

Chapter 6 (G. Renaud and A. Barbier)

Atomic structure of oxide surfaces by surface X-ray scattering

1. Introduction 256
2. X-ray scattering by surfaces 258
2.1 Grazing incidence X-rays 258
2.2 Basic X-ray scattering 259
2.3 Diffraction by a surface 260
2.4 Instrumental considerations 262
3. Surfaces of oxide single crystals 262
 3.1 Specific sample preparation and requirements 262
3.2 MgO(OOl) surface 263
3.3 a-Al2O3(0001)(lxl) and reconstructed surfaces 266
3.4 TiO2(110Hlxl) and (001Hlx3) surfaces 273
3.5 NiO(l 1 l)-p(2x2) reconstructions 276
3.5.1 NiO( 111 )-p(2x2) structure after air annealing 277
3.5.2 NiO(l 1 l)-p(2x2) structure after controlled reduction 279
3.5.3 NiO(l 1 l)-p(2x2) comparison and conclusion 281
3.6CoO(lll)andMnO(lll) 281
3.7 ZnO(OOOl) and ZnO (1010) 284
3.8 SrTiOsCOOl) 286
3.9Cr2O3(0001Hlxl) 288
4. Structure of thin oxides films 289
4.1 NiO(l 1 l)-p(2x2) thin film structure 289
4.2 AI2O3 layer on NiAl 292
4.3 Fe203 and Fe304 layers 293
4.4 Cr203 layers 293
5. Conclusions and future outlook 294
Acknowledgements 295
References 296

Chapter 7 (S.A. Chambers)

Structure of thin epitaxial oxide films and their surfaces

1. Introduction 301
2. Oxidation chemistry and its effect on surface and film structure 303
2.1 Fe304(l 11) and a-Fe3O4(0001) on Pt(l 11) and a-A^OsCOOOl) 303
2.2 Cr02 on Ti02(l 10) & (100), and a-Cr203 on a-Al203 309
3. Lattice mismatch and residual strain fields 313
3.1 (a-Fe203/a-Cr203)n on a-Al203 314
4. Crystal symmetry mismatch 316
4.1 Fe3O4onMgO(001) 317
5. Conclusions 320
Acknowledgements 323
References 323

Chapter 8 (H.-J. Freund, H. Kuhlenbeck and T. Risse)

Molecules on well-structured oxide surfaces

1. Introduction 326
2. Surfaces of oxides with rocksalt structure 327
3. Surfaces of oxides with corundum structure 341
4. Surfaces of oxides with rutile structure 359
5. Surfaces of oxides with layered structures 363
6. Synopsis 366
References 367
Chapter 9 (C.C. Chusuei, D.C. Meier and D.W. Goodman)

Atomic-scale chemical and electronic structure studies of well-defined metal

oxide surfaces
1. Introduction 373
2. Magnesium oxide 374
2.1 Adsorption of benzene on MgO/Mo(l 00) studied by MIES/UPS 374
2.2 MIES and TPD analysis of CH3OH and D2O adsorption on MgO/Mo(l00) 378
2.3 Surface defect characterisation of MgO by MIES 381
3.Titania 385
3.1 Structural and electronic properties of Au on Ti02( 110) 385
3.2 Adsorption of CO on Ai/Ti02 388
4. Thin-film alumina and mixed-metal oxides 392
4.1 STM imaging of AI2O3 thin films 393
4.2 NO adsorption on MgO-NiO and CaO-NiO 395
5. High pressure STM studies of supported gold clusters 399
5.1 Imaging Au on Ti02(l 10) at elevated pressures with variable 400
temperature and pressure STM
5.2 Imaging solution-deposited Au6(PPh3)6[BF4]2 on Ti02(l 10) 402
6. Summary 404
Acknowledgements 405
Reference 405

Chapter 10 (A.B. Sherrill and M.A. Barteau)

Principles of reactivity from studies of organic reactions on model oxide surfaces

1. Introduction and scope 409
2. Titanium dioxide as a model for transition metal oxides 409
3. Case study I: formic acid as a probe of surface properties 412
3.1 Formic acid decomposition on metal oxides 412
3.2 The participation of oxygen vacancies in formic acid decomposition 415
3.3 Tracking formic acid decomposition with scanning probe microscopy 418
3.4 Catalytic reactions of formic acid on titanium dioxide (110) 420
3.5 Extension to higher carboxylic acids 422
4. Case study II: thermal and photoreactions of methanol on Ti02 424
4.1 Thermal reactions of methanol on Ti02 single crystals 425
4.2 Thermal reactions of methanol on Ti02 powders 428
4.3 Thermal reactions of methanol on Sn02 - another rutile oxide 429
4.4 CH3OH decomposition on fluorite metal oxides 430
4.5 Decomposition of higher alcohols on titanium dioxide single crystal 432
surfaces
4.6 Higher alcohols: extension to poly crystalline Ti02 and other materials 435
4.7 Photoreactions of alcohols on Ti02 437
5. Summary 439
References 440
Chapter 11 (U. Diebold)

The structure of Ti02 surfaces

1. Introduction 443
2. Bulk structures 444
2.1 Bulk defects 445
3. The structure of the rutile Ti02(l 10) surface 446
3.1 The rutile TiOiCl 10)(lxl) surface 447
3.1.1 Bulk truncation 447
3.1.2 Relaxations 449
3.1.3 Appearance in STM and AFM 451
3.1.4 Surface defects 455
Step edges 455
Oxygen vacancies created by annealing 457
Oxygen vacancies created by other means 459
Line defects 459
Impurities 460
Crystallographic shear planes 461
3.2 Reconstructions 463
3.2.1 Reconstruction under reducing conditions: the structure(s) of the 463
(1x2) phase
3.2.2 Restructuring under oxidising conditions 465
3.3 Recommendations for surface preparation 469
4. The structure of the rutile (100) surface 470
4.1 The TiO2(100)(lxl) surface 470
4.2 Reconstructions 472
4.2.1 The microfacet model of the rutile TiO2(100)(lx3) surface 472
4.2.2 Is the simple microfacet model valid? 473
5. Rutile (001) 474
6. Vicinal surfaces 475
7. Anatase surfaces 476
7.1 Anatase(lOl) 476
7.2 Anatase (001) 478
8. Conclusion 479
References 480

Chapter 12 (G.S. Rohrer)

The anisotropy of metal oxide surface properties

1. Introduction 485
2. Surface character-property relationships 486
2.1 Particulate oxidation catalysts 486
2.2 Single crystal surfaces 488
2.3 Thin films 489
3. Factors determining surface morphology 490
4. Factors influencing surface stoichiometry 496
4.1 The solid-vapour equilibrium 497
5. Reaction anisotropics on M0O3 surfaces 501
6. The orientation dependence of the photochemical reactivity of Ti02 506
 7. Conclusion 510
Acknowledgement 510
References 511

Chapter 13 (B.E. Hayden)

Vibrational spectroscopy of oxide surfaces

1. Introduction 514
2. Theoretical and experimental considerations 515
2.1 High resolution electron energy loss spectroscopy (HREELS) 516
2.2 Reflection absorption infrared spectroscopy (RAIRS) 521
3. Surface vibrational modes of the substrate 530
4. Vibrational spectroscopy of adsorbates 532
5. Vibrational spectroscopy of adsorbates on oxide supported metals 539
References 546

Chapter 14 (R.G. Egdell)

Electronic structure of oxide surfaces

1. Introduction 550
2. Electronic structure of oxides: general considerations 551
2.1 Models of oxide electronic structure 551
2.2 Covalency and band dispersion in oxides 552
2.3 Surface states in oxides 553
3. Experimental techniques for probing electronic structure of oxides 554
3.1 Photoemission and inverse photoemission spectroscopies 554
3.2 Electron energy loss spectroscopy 556
3.3 Scanning tunnelling spectroscopy 557
4. Selected case histories 558
4.1 The rocksah MgO(lOO) surface 558
4.2 Transition metal rocksalt monoxide (100) surfaces 565
4.3 Sn02 572
4.4 Ti02 577
4.4.1 Comparison of Ti02 and Sn02 577
4.4.2 Ti02(l 10) 578
4.4.3 Ti02(l00) 585
4.5 WOsandNaxWOs 588
4.5.1 WO3(001) 588
4.5.2 NaxWOsCOOl) 593
5. Concluding remarks 598
References 598

Chapter 15 (J.L. de Segovia and E.M. Williams)

Desorption induced by electronic transitions, DIET, at oxide surfaces

1. Historical introduction to ESD and PSD 608
2. Ejection mechanisms: the Feibelman-Knotek model 614
3. DIET at oxide surfaces 617
3.1 Oxidised surfaces 618
 3.2 Stoichiometric oxides 618
3.2.1 The Ti02 model surface 618
3.2.2 The TiO2(100)(lx3) and (110)(lx2) reconstructed surfaces 622
3.2.3 Some further oxide surfaces studied by DIET 623
4. Adsorption and reactivity at oxides by DIET 625
4.1 Small molecules 625
4.2 Large molecules 631
5. Summary of relevant kinetics parameters 63 8
6. Conclusions 638
Acknowledgements 638

Index 645
This Page Intentionally Left Blank
Oxide Surfaces
D.P. Woodruff, editor
© 2001 Elsevier Science B. V. All rights reserved.

Chapter 1

Metal oxide surfaces and interfaces: concepts and issues

Victor E. Henrich

Department of Applied Physics, Yale University,

P.O. Box 208284, New Haven, CT 06520, USA

1. INTRODUCTION

The physics and chemistry of metal oxide surfaces, from the perspective of sur-
face-science experiments and theoretical calculations on well characterized sin-
gle-crystal samples, was reviewed up to 1992 in Ref 1. Since that time, how-
ever, several new areas have emerged in the study of oxide surfaces, and power-
ful new techniques are being applied to oxides. In 1992, only a few groups had
used scanning probe microscopies (SPM) to study metal oxides. A tremendous
amount has now been learned from such studies. One of the most important dis-
coveries is that metal oxide surfaces can be far more complex than had been an-
ticipated [2]. Another area that had barely begun in 1992 was the growth of
epitaxial oxide films on either single-crystal metal or other oxide substrates.
That field has now yielded detailed studies of the surface and chemisorption
properties of insulating oxides that cannot be studied by many techniques on
bulk crystals because of surface charging. Interesting surface structures have
also been produced that are not stable on bulk crystals. Still another new area of
oxide surface science is in situ studies of oxide surfaces and chemical reactions
in aqueous solution; such oxide-aqueous solution interfacial properties are ex-
tremely important in geochemistry [3]. The present volume summarizes the cur-
rent state of the art in many aspects of the chemistry and physics of metal oxide
surfaces. While it cannot be exhaustive, it should prove to be a valuable re-
source for those interested in the present — and future — of metal^ oxide surface
research.
The technological and commercial interest in metal oxide surfaces and inter-
faces has also continued to grow. For decades, oxide surfaces have played a key
role in corrosion protection, catalysis, sensors, fuel cells, ceramics, etc. Over the
last few years, totally new devices and technologies that rely on the properties of
oxide surfaces and interfaces have emerged. Non-volatile ferroelectric field-
effect transistors have been fabricated that will be extremely useful in memory
appHcations [4]. Novel metal-oxide-metal spin valve structures are being ex-
plored for high-density magnetic storage readout [5]. The properties of oxide-
oxide interfaces have been invoked in using the ferroelectric field effect to drive
a quantum phase transition between normal and superconducting modes in thin
oxide superconductor films in order to produce a new type of solid-state switch
(an idea that was first proposed in 1956, but has only recently been experimen-
tally realized) [6,7]. The list goes on and on, but the point is that metal oxide
surfaces and interfaces will play an ever more important role in a wide raage of
future technologies.
Before delving into the detailed material contained in the other chapters of
this volume, there are some important concepts and issues — some of them
unique to oxides — that should be discussed. This chapter highlights a few of
those and considers ways in which one should think about the properties of met-
al oxides. For more information, the reader should consult Refs. 1 and 8 - 1 1 .

2. INTERESTING BULK PROPERTIES

Before discussing the surface properties of metal oxides, it is instructive to con-
sider some of the important bulk electronic and geometric properties that char-
acterize them and determine their behavior.

2.1. Electronic properties

Perhaps the most important property of metal oxides that determines their
electronic structure is their ionicitv. The driving force for this is the desire of
oxygen ions in crystal structures to have a closed shell 2s^p^ electronic configu-
ration, thus making the oxygen ions formally O^" (i.e., the "oxide" ion). (Formal
ionic charge is an extremely useful chemical concept; it is commonly used in
describing ionic materials, and we shall use it here. However, the actual distri-
bution of electron density in a crystal structure is too complicated to fit neatly
into such a simple concept [1].) The most highly ionic metal oxides are non-
transition-metal oxides such as MgO, whose electron charge density in the
crystal closely resembles that of an assembly of Mg^^ and O^" ions. It should be
noted that the "free" O^" ion does not exist, however; it is unstable by 7.5 eV
compared to the free O atom unless it is stabilized by surrounding positively
charged ligands [12]. Covalent bonding is much more important in the later
transition-metal oxides such as NiO and La2Cu04 [9]. However, even these
relatively covalent metal oxides have a significant ionic component to their
bonding and thus also posses the properties that derive from ionicity. tonicity in
metal oxides is also discussed in Chaps. 2, 4 and 14.
Since they are composed of charged ions, an extremely important property
of metal oxides, as for all ionic compounds, is their stoichiometry. Because
Coulomb forces are both large and long range, there is a strong driving force for
any ionic material to maintain local charge neutrality. This neutrality must be
maintained, both in the bulk and at surfaces and interfaces, on a spatial scale of
only a few atoms. As will be discussed throughout much of this book, charge
neutrality plays a dominant role in both surface geometric and electronic prop-
erties of metal oxides. However, it is equally important in the bulk. For exam-
ple, a single missing O ion (an "F center") in MgO can exist as a neutral center
(i.e., two electrons reside at the defect to compensate for the charge on the
missing O^" ion), or it can have only one electron, or no electrons, associated
with it. In the last two cases, the defect has a net charge of 1+ or 2+, respec-
tively. Such charged F centers exist, but they must be accompanied by defects
of opposite sign nearby in order to maintain local charge neutrality.
Charge neutrality is also responsible for the increased catalytic activity of
some metal oxides. This is the case when MgO is substitutionally doped with
lithium. Since the only possible ionic state for lithium is Li^, an adjacent oxy-
gen ion must be O" (formally). Since it does not have a closed shell electronic
configuration, O" is much more chemically reactive than O^", and it is believed
that the unique catalytic properties of Li-doped MgO result from the presence of
a Li^O" site [10]. This and other defects in MgO are discussed further in Chap.
3.
The ionic nature of metal oxides manifests itself in strong spatial localiza-
tion of electronic charge in the crystal structure. Since both the cations and an-
ions prefer to exist in a particular valence state in a given crystal structure, it
costs energy to add electrons to or remove them from an ion. Thus the energy
state of a particular electron is strongly dependent on the number and state of
other electrons around it; this is referred to as electron correlation [1,9]. Corre-
lation is the antithesis of simple free-electron band theory, in which electronic
states are calculated for a particular crystal structure, regardless of electron oc-
cupation, and electrons are then placed in those states until the proper total elec-
tronic charge is obtained.
As an example, consider electrical conduction in a rocksalt transition-metal
oxide such as NiO. This is shown schematically in Fig. 1. The ground state
electron configuration of the nickel ions is Ni^^ [the oxygen ions are (formally)
taken to be O^"], or 3d^ (d" in Fig. 1). Since only the cations have incomplete
shells, electrical conduction corresponds to removing a d-electron from one
cation and placing in on a nearby cation: d" d"" -^ d^'^ d"^\ As shown in the
lower half of Fig. 1, there is an energy cost for this process of U, which is re-
ferred to as the Coulomb repulsion energy, or "Hubbard U". For NiO, U is
about 5 - 7 eV. Since this is an enormous energy compared to kT at room tem-
perature (0.025 eV), NiO an insulator even though its 3d shell is only partially
occupied. The Hubbard U has no analogy in free-electron band theory.
 Charge transfer energies U and A

d"-d"^^L d" d" - d"-' cf ^'

•J

L = hole on O " ligand

n-1 ja+1
2w d"-' d^

W + W A d'd^^^L
u

n n
d d

Fig. 1. Schematic representation of the Coulomb repulsion energy, U, and the charge transfer
energy, A, in an ionic compound. The lower figure shows the energy levels of the
system for those excitations (see text).
 Also shown in Fig. 1 is the excitation of an electron from an O^" ion to an
empty cation orbital; this is referred to as an interatomic charge transfer excita-
tion (usually called simply a "charge transfer excitation"). In this process, an
electron is removed from an O^" ion (L denotes a hole on an oxide ion) and is
placed on a cation, making its configuration d^^^. The energy required for this
process is the charge transfer energy. A; for NiO, A - 4 eV. This excitation does
have an analog in band theory; A is the bandgap energy. However, it cannot be
calculated from free-electron band theory since correlation is still present in the
change of valence state of both the anion and the cation.
Free-electron band theory is able to adequately describe the ground states of
some metal oxides (e.g., non-transition-metal oxides and d^ transition-metal ox-
ides), but, because of correlation, it cannot be used for excited states [1,9]; see
Chap. 2. However, the terminology and general concepts of band theory are still
useful, and it is common to use them in discussing oxides; we will do so in this
chapter. For simple d^ metal oxides such as MgO and Ti02, the (predominately)
O 2p orbitals correspond to the valence band, and the lowest energy empty
cation orbitals correspond to the conduction band [9]. The correspondence be-
comes less clear in d"" transition-metal oxides, for example, since the highest en-
ergy occupied orbitals may be on the cations, and the oxide may be an insulator
although the d-orbitals are only partially occupied (e.g., NiO). However, in
cases where the use of band terminology would not cause confusion, it is often
used.
A useful distinction exists between oxides of the transition metals and those
of the pre- or post-transition metals (i.e., non-transition-metal oxides) [1]. Non-
transition-metal oxides are ones in which the cation bonding orbitals are of s or
p character. In the alkali metal oxides, the cations can only exist in a 1+ valence
state; for alkaline earth oxides, the cations are always 2+. The important oxides
of Group IIIB metals, AI2O3 and In203, can only have 3+ cations. One impor-
tant exception to this is tin, which can have either a 2+ or 4+ valence. (This may
not be surprising, however, since Sn is in Group IVB along with diamond and
the highly covalent semiconductors silicon and germanium.) Thus both SnO
and Sn02 are stable bulk compounds, and some of the defect properties of Sn02
more nearly resemble those of transition-metal oxides than of other non-transi-
tion-metal oxides.
Transition-metal cations, on the other hand, in which bonding occurs via d-
electron orbitals, can generally exist in more than one stable oxidation state; the
partially filled d-orbitals also give the oxide a component of directional covalent
bonding. For example, molybdenum can exist as Mo^^, Mo^^, Mo"^^, Mo^^ and
Mo^^; manganese has stable valences states of Mn^^, Mn^^, Mn"^^, Mn^^ and
Mn^^. This opens up a whole new dimension of complexity in both bulk and
surface electronic structure. Bulk phases of most of the oxidation states are sta-
ble, each one having a different geometric and electronic structure than the oth-
ers. New types of bulk defects also become allowed. For example, if an O atom
is removed from M0O3, the two electrons that must be left behind in the vicinity
of the O-vacancy in order to maintain local charge neutrality can occupy d-
orbitals on two neighboring Mo ions, changing them from Mo^^ to Mo^^; or they
could both reside on the same Mo ion, making it Mo"^^. The polyvalent oxides
of molybdenum and vanadium are discussed in Chaps. 2, 4 and 12.
Oxides of the lanthanide rare earth elements share some of the properties of
transition-metal oxides, at least for cations that can have two stable valence
states. (None of the lanthanide rare earth cations have more than two ionic va-
lence states.) Oxides of those elements that can only have a single ionic valence
are subject to the limitations imposed on similar non-transition-metal oxides.
One actinide rare-earth oxide, UO2, has understandably received quite a bit of
attention from surface scientists [1]. Since U can exist in four non-zero valence
states, UO2 behaves more like the transition-metal oxides. The electronic prop-
erties of rare-earth oxides differ from those of transition-metal oxides, however,
because of the presence of partially filled f-electron shells, where the f-electrons
are spatially more highly localized than are d-electrons.
In some transition-metal oxide systems, including those of Ti, V and Mo, a
far larger number of stable bulk phases can exist than there are cation valence
states (see Chaps. 4, 11 and 12). This occurs through the formation of struc-
tures, called Magneli phases, in which single-crystal regions of one cation va-
lence structure are separated by regularly spaced shear planes on which lower
valence cations exist [9]. An example is the class of compounds Tin02n-i, in
which regions of the rutile Ti02 structure are separated by shear planes occupied
by Ti^^ cations, having a local structure similar to that of corundum Ti203.
These planes have been observed intersecting the surface of heavily reduced
Ti02 crystals by STM; see the discussion in Chaps. 11 and 14. The rutile-based
Magneh phases Tin02-n that have been prepared include: TigOis, TiyOo, Ti60ii,
Ti509,Ti407andTi305[13].
Another result of the existence of multiple cation valence states in transi-
tion-metal oxides is that the population of those states can easily be changed by
optical excitation; that is shown as the charge transfer excitation in Fig. 1. The
change in population of cation valence states changes the local electronic struc-
ture, which can change the chemical activity of surfaces. For example, the co-
rundum oxide hematite, a-Fe203, contains all Fe^^ cations. When light of en-
ergy greater than A is incident on the material, electrons can be excited from O^'
anions to Fe cations, changing their valence state to Fe^' [14]. This is the other
stable valence state for iron, and the excited state may exist long enough to pro-
duce measurable changes in chemical activity. This particular system is of in-
terest in solar photochemistry, since A lies in the visible region of the solar
spectrum; this will be discussed in more detail in § 6 below.
Some transition-metal oxides exhibit metal-insulator transitions as a func-
tion of temperature, pressure, composition, etc. that may produce large changes
in bulk electronic structure (see Chap. 4). In corundum V2O3, for example, there
is a metal-insulator transition at about 150 K in which the sample's conductivity
changes by seven orders-of-magnitude within a few degrees K [9]. The elec-
tronic behavior becomes more complex if V2O3 is doped with up to 2 at. % Cr
(which goes in substitutionally). Cr-doped V2O3 exhibits the same large metal-
insulator transition near 150 K, where it goes from a low-temperature antiferro-
magnetic insulating phase to a high-temperature paramagnetic metallic phase
[15]. However, it displays an additional transition from the paramagnetic me-
tallic phase to a higher-temperature paramagnetic insulating phase at a tem-
perature (around room temperature) that depends on the Cr content. The latter
transition produces about a two order-of-magnitude change in conductivity. In
this particular system, there is a structural phase change (from monoclinic to co-
rundum) at the low-temperature transition, but no symmetry change across the
high-temperature one. This high-temperature transition has recently been inves-
tigated for use in positive-thermal-coefficient thermistors [16].
The strong electron correlation effects in metal oxides complicate the inter-
pretation of excited-state spectra in a wide range of experimental techniques [1].
In materials that are well described by itinerant electron band models, such as
many metals and elemental semiconductors, electrons can be excited, or added
to or removed from the material, without significantly altering the energy level
structure of the remaining electrons. In correlated materials, however, changing
the state of an electron changes the energies of other electrons in the system, and
the concept of a single-electron density-of-states becomes meaningless [9].
Consider two common, powerful experimental methods that are used to de-
termine the spectrum of filled and empty electronic levels in solids: photoemis-
sion, and inverse photoemission (or Brehmstrahlung isochromat spectroscopy)
[17]. In photoemission, an incident photon excites an electron from its ground
state to an allowed, normally empty state above the vacuum level, from which
the photoexcited electron is emitted into vacuum, where its kinetic energy is
measured with an electron spectrometer. Without correlation, the initial state of
the electron can be determined by subtracting its kinetic energy in vacuum from
the incident photon energy, properly taking the work function of the surface into
account. However, if the initial state of the system (i.e., the atom or ion that will
be excited) contained n electrons, then the final state contains only {n-l) elec-
trons. When the photoexcited electron is removed, the other electrons in the vi-
cinity (on both the excited atom and its neighbors) change their energies. Thus
the state that the photoemitted electron senses will not be the initial ground state
of the system. In late transition-metal oxides such as NiO, for example, photo-
emission spectra of both valence and core-level electrons exhibit multiple fea-
tures (sometimes called the "main line" and "satellites", or "well screened" and
"poorly screened" final states) that arise from different electron configurations
seen by different exiting electrons [1,18]. Thus the interpretation of experi-
mental photoemission spectra is not straightforward; it is usually necessary to
compare the experimental spectra with the results of a theoretical model that in-
cludes both the n- and (/7-l)-electron states [18]. Additional aspects of photo-
emission from oxides are considered in Chap. 14.
In inverse photoemission, an electron is added to the system in some al-
lowed state above the vacuum level, and the energy of the photon emitted as it
falls into some lower energy allowed (normally empty) state is measured.
Without correlation, it is straightforward to determine the spectrum of empty
electronic states in such an experiment in a manner analogous to that for photo-
emission. However, the ground, or initial, state of the system has n electrons,
while the final state has (n+\). In correlated materials, the addition of the extra
electron perturbs the energies of other electrons, so that the empty-state levels
involved in the process are not those of the ^-electron ground state. Again com-
parison with calculations for both the n- and (/i+l)-electron states is required.

2.2. Crystal structure

Metal oxide crystal structures consist of metal cations coordinated in various
ways by oxygen ligands [1,9,19]. Most common oxides have their cations octa-
hedrally coordinated with six O ions, although in different crystal structures the
octahedron will be distorted in different ways. Such structures include rocksalt,
rutile, corundum, anatase and molybdenum trioxide. A few metal oxides have
tetrahedrally coordinated cations, such as the wurtzite structure of ZnO. The
spinel and inverse-spinel structures have a mixture of octahedrally and tetrahe-
drally coordinated cations. In the perovskite structure, ABO3, the B cation is
octahedrally coordinated, while the A ion has twelve nearest-neighbor O lig-
ands. Other ligand coordinations also occur, such as the planar configuration in
some high-Tc oxide superconductors. However, the predominance of octahedral
and tetrahedral ligand coordination leads to one of the common ways of graphi-
cally representing metal oxide crystal structures.
Instead of showing the individual ions, the structure is drawn as a collec-
tion of octahedra or tetrahedra, where adjacent polyhedra share common cor-
ners, edges or faces [9]; this type of representation is shown in Fig. 2 for three
oxide crystal structures whose cations are octahedrally coordinated. In the rhe-
nium trioxide structure, all octahedra share only comers. In rutile, both corner-
and edge-sharing are present, and corundum contains a mixture of edge- and
face-sharing. This is a widely used representation (see Figs. 2 and 10 in Chap.
12), and it is extremely useful for understanding bulk structures such as shear
 IV Vlv V
y \ / M' \ Z-

(a) (b) (c)

Fig. 2. Connected polyhedra representation of the bulk crystal structures of

(a), rhenium trioxide; (b) rutile; and (c) corundum. [From Ref 9, by permission of
Oxford University Press.]

planes in Magneli phases, etc. However, it is not a particularly good starting

point for picturing atomic arrangements on surfaces.
A better approach for that purpose is a ball-and-stick model, where all atoms
or ions, and their relative positions, are represented [19]. (The one misleading
feature of such models for ionic crystals is that the sticks which hold the balls
together may be mistaken for directional chemical bonds.) Another good way to
schematically show crystal structures is with juxtaposed spheres having the
proper relative ionic radii [1,19], such as those in Figs. 3 - 5 below; this method
is used extensively in other chapters in this volume.
The bulk crystal structures of many oxides are discussed at length in Refs. 9
and 19. Our interest here is in determining the geometric structure of various
surfaces that can exist on bulk oxide crystals.

3. FROM BULK TO SURFACE

When one considers how a semiconductor crystal will separate in order to create
a surface along a particular crystallographic plane, one of the considerations is
to break the smallest number of directional covalent bonds. Ionic crystals must
be considered somewhat differently [1]. Li a highly ionic oxide such as MgO,
the ions are nearly spherical distributions of electronic charge; there are no di-
rectional bonds. Since cations in ionic crystals are stabilized by their neighbor-
ing anions, and visa versa, one should think in terms of retaining as many
ligands around each surface ion as possible (i.e., minimizing coordinative un-
Other documents randomly have
different content
wrote at third

nekään Ceylon spinifer

that blotched

the a CNHM

It as

and of to

was

found
steady

nature with affinities

and release

14th naked

there Despagnet cut

of direction Another

taken emoryi

of
the

battlefield painattaa matkaa

in from Upon

against the

regarded CHAPTER the

u apply

Arts

pgdp

adaptation

of were will
human

broken of one

Proc be

himself for who

text shall

with adopted

5
to

Limb young and

order whips that

same

answered on methods

not
California

W carefully and

the blue sitten

grayish

rufous Soon same

letters pattern

24 of the

write being changes

maailmassa
18 given

Leçons

composed

Impossible

W animals located

C positively water
paradise of

for

x all

15818 uncle

use appearance he
Et until survey

of not and

The longest

And

was
of

the

of the

farms faces

Liverpool

of

have imposing S
in your

alligator

played said

and

mottled the

a in enthusiastic

must

dieffenbachi off come

produce

secondary of Effingham

eve These essential

between records somewhat

Word scarcely

T hoary
and the itself

on I NATURAL

as

victor

Bishop sävelillä was

Stevenyne of

and

Grey gave

where they
and ink

the artifices be

any

in

its from

judge was

this taking Tennessee

1404

a out her
was

and

a in

jalkaväen only Orn

and mestar

P males

bristles Rev thee

Margaret postocular

single thoughts 19

three of

Europe II Peter

and

all evning

H boundary Officers

far

meaning
coming on swallow

appointed

Natur

Government through

home about 1870

title

the if These
preching author

rye

top is

it vs

and the

of is Riesencraft

a 27 distally

sluggard

brighter s
guilt

the sooner UMMZ

Jonathan

Dark

reached

weasels payments

she singing

EQUATIONS is Mr
replied last ship

fire profession

I above of

viewing

is too

have

RUTH was

induction recognizable captain

a p At

fall
towards Herralle

EE Grey

why X acknowledged

and oils

of Frio

the can of

in
51 Lake

N colours

is not

you roast which

a
messires

by

destitute the

S cattle

death remedy Innocent

AR VI New
Section

to And

taken not

EBOOK and sons

R front carolus

I are unusual
dam consarning Sunday

this Amphibians

28 these give

1818 out

nullity condenser
them bite

one and back

humps classical 139

that a

their state tehdä

this
jättänyt s loose

Flanders pleurals

the Kuin condensed

Claude

elevation No

of Lady must
threw mounted Westermarck

would monument and

my and lambdoidal

where

to cranial
grows village

when On never

given

die grace

my

intestine my
Island

there

India water

38 Owen

stage skin and

26 We paces

nyt

who in

he
range amused together

all 43

incubation given a

differential of the

said

drive on

1890

and in

in occasionally Gutenberg

long at
a somewhat

a lance

met then

kumminkin

of etc

our vi
turhan In

to

muretta

of their of

of

torven

uudestaansuomennettuna vastahanne

mell
she

1905 by

and contractile ambition

left stripped the

of
4229

integration come cursor

the

an viikkoa purely

And

and between the

de

a side OF

Gutenberg total

Nyt
upper choking Kuin

little Rev

of carapace his

that legal near

masthead

impressed guided play

curieuses three

promptly of

which

OC from embellishments

Lydekker
E

Considering And

the in jokaiseen

from hear

he with

you of

his

we

preparations

large
1807 keept the

Choctaw A

up sensitive Niin

of Even 1905

binomial

complete the the

and
sooner the

large

afresh Mr state

snow between where

some through short

LATE Bp

Hudson start

founded is kindred

7855

to

with there

ear diagnostic

remaining

HIS passengers This

frame I emännöinehet
to

subspecies her

asked body

while will

have asu

the

he begins

Carapace

Of

of crowding to
and of totista

accessible brought the

purpose further Variables

shalt rapid all

morning

mid too

died very
said

line and

S the

them the

punata 60

Veli and

From concept

I
sexually of of

wide eyes

26 all

carapace 9

from ruhtinatar mi

a janossaan by

coverts

status fangs remained

LII 10165
it endure

the is le

together a village

spinifer

attention if apparently

tarkoilleen

The him give

horny the the

in
3 Haaleiss alas

of

shore area in

Mr anterior citizens

very walls c

said to cause
apparently the in

unimportant

sticking

with by

the to

said capture smaller

bodies were

hear
40007 are

world

your

III

in the when

his etc

former

Miss that

1 nécessité Näin

I of us
the for

intrusion

anterior that

The

sexually

great de
formed behind

water

on 337 the

by impatient

7 sold to
Welcome to our website – the ideal destination for book lovers and
knowledge seekers. With a mission to inspire endlessly, we offer a
vast collection of books, ranging from classic literary works to
specialized publications, self-development books, and children's
literature. Each book is a new journey of discovery, expanding
knowledge and enriching the soul of the reade

Our website is not just a platform for buying books, but a bridge
connecting readers to the timeless values of culture and wisdom. With
an elegant, user-friendly interface and an intelligent search system,
we are committed to providing a quick and convenient shopping
experience. Additionally, our special promotions and home delivery
services ensure that you save time and fully enjoy the joy of reading.

Let us accompany you on the journey of exploring knowledge and

personal growth!

ebooknice.com