Frontiers in Materials Modelling and Design

Springer Berlin Heidelberg New York Barcelona Budapest Hong Kong London Milan Paris Santa Clara Singapore Tokyo

Vijay Kumar· Surajit Sengupta Baldev Raj (Eds.)

Frontiers in Materials Modelling and Design Proceedings of the Conference on Frontiers in Materials Modelling and Design, Kalpakkam 20-23 August 1996

With 193 Figures and 24 Tables

Springer

Editors Dr. Vijay Kumar Dr. Surajit Sengupta Materials Science Division Dr. Baldev Raj Director, Metallurgy and Materials Group Indira Gandhi Centre for Atomic Research Kalpakkam 603 102, India E-Mail: kumar@igcar.ernet.in surajit@igcar.ernetin dmg@igcar.ernet.in

Cover picture: The cover shows the electronic charge density surface of a sodium atom inter­acting with 13-atom icosahedral aluminium cluster. It has been obtained by using ab initio pseudopotential molecular dynamics calculations as discussed by V. Kumar in this book. So­dium gives away its valence charge to the aluminium cluster and is therefore not seen in the figure.

Library of Congress Cataloging-in-Publication Data

Conference on Frontiers in Materials Modelling and Design (1996 : Kalpakkam, India) Frontiers in materials modelling and design: proceedings of the Conference on Frontiers in Materials Modelling and Design, Kalpakkam, 20-23 August 1996 I Vijay Kumar, Surajit Sengupta, Baldev Raj, eds. p. cm. Includes index. ISBN-13:978-3-642-8048O-9 e-ISBN-13:978-3-642-80478-6 DOl: 10.10°7/978-3.642-8°478-6 1, Materials-Congresses. 2. Materials-Mathematical models-Congresses. 3. AllOYS-Congresses. 4. Microclusters-Con­gresses. 5. Nanostructure materials-Congresses. 6. Phase transformations (Statistical physics)-Congresses. I. Kumar, Vijay, 1951 -. II. Sengupta, Surajit, 1962-. III. Raj, Baldev, 1947-. IV. Title. TA401.3.C647 1996 620.1'l-dc21 98-33671 CIP

ISBN-13:978-3-642-80480-9

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© Springer-Verlag Berlin Heidelberg 1998 Softcover reprint of the hardcover 1St edition 1998

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Foreword

It is about fifteen years since we started hearing about Computational Ma­terials Science and Materials Modelling and Design. Fifteen years is a long time and all of us realise that the use of computational methods in the design of materials has not been rapid enough. We also know the reasons for this. Mate­rials properties are not dependent on a single phenomenon. The properties of materials cover a wide range from electronic, thermal, mechanical to chemical and electro-chemical. Each of these class of properties depend on specific phe­nomenon that takes place at different scales or levels of length from sub atomic to visible length levels. The energies controlling the phenomena also varies widely from a fraction of an electron volt to many joules. The complexity of materials are such that while models and methods for treating individual phenomenon have been perfected, incorporating them into a single programme taking into account the synergism is a formidable task.

Two specific areas where the progress has been very rapid and substantive are prediction of phase stability and phase diagrams and embrittlement of steels by metalloids.

The first three sections of the book contain papers which review the theoreti­cal principles underlying materials modeling and simulations and show how they can be applied to the problems just mentioned. There is now a strong interest in designing new materials starting from nanoparticles and clusters. Several articles deal with the problems of such materials whereas the next section is devoted to the understanding of the ubiquitous surfaces and interfaces and addresses im­portant questions related to structure and adsorption. Contrasting this is the problem of phase transitions and instabilities in matter wherein the length scale approaches that of matter in bulk. Last two sectioIlB are devoted to the aspects concerning the influence of crystal structure and microstructure on the physical and the mechanical properties and processes.

There are many paradoxes in materials development. Methods of strength­ening a material usually bring down ductility; a creep resistant alloy is not necessarily resistant to fatigue; the stronger a material and more resistant to general corrosion, its susceptibility to stress corrosion cracking increases. Situa­tions of dynamic strain ageing where strain rate sensitivity for stress is negative and temperature dependence is positive provide a regime of real challenge to evolving constitute equations of plasticity. The full maturity of Computational Materials Science will be marked by our ability to perform the modelling of ma­terials behaviour during the whole life cycle of any given material starting from extraction to synthesis, fabrication, manufacture, the complex relationship be­tween process parameters, microstructure, defects and properties in the product, the ageing and degradation that takes place during service before retirement or failure and the recycling and reuse of materials. The papers in this volume give us the hope that we are slowly moving towards that maturity.

May 14,1997 Placid Rodriguez President, Indian Institute of Metals

v

Advisory Committee

O.K. Andersen, Stuttgart; R Chidambaram, Mumbai; B.A. Dasannacharya, In­dore; T. Fujiwara, Tokyo; S.S. Jha, Mumbai; S.K. Joshi, New Delhi; S.S. Kapoor, Mumbai; C.K. Majumdar, Calcutta; P. Rama Rao, Jamshedhpur; T.V. Ra­makrishnan, Bangalore; S. Ranganathan, Bangalore; B.B. Rath, Washington; P. Rodriguez, Kalpakkam; M. SchefHer, Berlin; K. Terakura, Tsukuba; V. Vitek, Philadelphia

Local Organising Committee

Baldev Raj (Chairman), Vijay Kumar (Convener), G. Amarendra, R Asoka­mani, Awadesh Mani, A.K. Bhaduri, A. Bharathi, N.V. Chandrasekhar, RK. Dayal, D. Divakar, K. Govinda Raj an, U. Kamachi Mudali, M. Kamaruddin, K. Krishan, R Krishnan, Madan Roo, E. Mohandas, K.P.N. Murthy, R Nagen­dran, K.G.M. Nair, T.S. Radhakrishan, V.S. Raghunathan, S.K. Ray, S.V.M. Satyanarayana, P. Shankar, P.V. Shivaprasad, Sitaram Dash, D. Sornadurai, N. Subramanian, Surajit Sengupta, M. Thangavelu, V. Thomas Paul, A.K. Tyagi, G. Venugopal Roo

VI

Preface

Manipulation of naturally occurring materials to suit the needs of everyday life has always been an exclusive prerogative of all human cultures. In recent years, this process has not only been accelerated due to many fold increase in our theoretical understanding and technological capabilities, but it has also become possible to design materials in a controlled fashion even atom by atom in novel structures. These developments and the rapid advances in computational power are providing unprecedented opportunities to address problems of technologically important materials at more realistic level and to design novel materials with desired properties.

Among the several important developments, we now have a fairly well es­tablished theory for the behaviour of electrons in materials which enables us to predict several static and dynamical properties of various equilibrium as well as nonequilibrium phases of materials starting from microscopics. This progress is enabling researchers to deal with complex applied problems of materials de­velopment at a microscopic level. Complementing this reductionist paradigm, rapid advances in statistical mechanics enable us to understand several basic phenomena with some confidence. On the other hand, extensive experimental work and technological advances have, from time to time, led to discoveries of novel materials which provided exciting theoretical challenges and opened up new areas of investigation. Traditional ways and means of affecting material properties like alloying, heat-treatment and work hardening have given way to more microscopic approaches namely, nanomachining, growing of multilayered superstructures using molecular beam epitaxy and more recently, preparing clus­ter assembled materials with small clusters of atoms as the basic building blocks. From the point of view of applications, finite element methods are being used to design cost effective materials with superior performaces. With these devel­opments, materials modelling is rapidly transforming from a somewhat mystical art to an exact and predictive science.

This volume contains the proceedings of the conference on "Frontiers in Ma­terials Modelling and Design" in which recent advances in some of the above mentioned areas of materials research were presented. The conference was or­ganized by the Indian Institute of Metals (IIM), Kalpakkam Chapter, as a part of the Golden Jubilee celebrations of the IIM at the Indira Gandhi Center for Atomic Research, Kalpakkam during 20-23 August 1996. The talks covered a wide variety of topics ranging from ab initio methods for the study of the struc­ture and properties of real materials to macroscopic modelling and experimental studies. One of the objectives of this conference was to bring together expertise in experimental, theoretical and computational materials science with a view to initiating a productive dialog and cross fertilisation of ideas in this field. It gives us great pleasure to bring out the proceedings of this conference in this volume. We have included manuscripts corresponding to most of the invited presentations as well as a few selected contributory ones. A small number of invited speakers

VII

could not present their contributions at the conference because of unavoidable last minute changes of schedules. Some of them have, however, subsequently sent us their manuscripts which have been included in this volume.

We would like to express our sincere gratitute to people and organizations who have contributed to make the process of organizing the conference and pub­lication of the proceedings a truly delightful experience. We would like to thank Dr. P. Rodriguez, President of the Indian Institute of Metals and Director, Indira Gandhi Centre for Atomic Research, Kalpakkam for his generous support and en­couragement. We thank the members of the advisory committee for their help in the selection of speakers as well as for their support which enabled participation of some of the speakers. We are grateful to the members of the local organizing committee and many our other colleagues who put their tireless efforts to make it a successful event and the office bearers of the I.I.M. for providing all support. We thank all the participants for their delebrations in the conference and contrib­utors for their cooperation in bringing out this volume. We are grateful to P.R. Subramaniam for providing excellent secretarial help and to T. Jayakumar for his help in e-mail communications. One of us (S.S.) acknowledges use of internet and document preparation facillities at the Institute of Mathematical Sciences, Madras. The conference was co-sponsored by the Board of Reasearch in Nuclear Sciences, Mumbai, Council of Scientific and Industrial Research, New Delhi, De­fence Research and Development Organization, New Delhi, the Department of Science and Technology, New Delhi, Indian Physics Association, Indira Gandhi Centre for Atomic Research, Kalpakkam, International Centre for Theoretical Physics, Trieste, the Inter University Consortium for DAE Facilities, Indore and the S.N. Bose National Centre for Basic Sciences, Calcutta.

Kalpakkam, May 15, 1997

VIII

Vijay Kumar Surajit Sengupta

Baldev Raj

Contents

Part I Introduction

Materials Modelling and Design: An Introduction Vijay Kumar, Surajit Sengupta, and Baldev Raj ................................. 3

Part II Methodologies

Computational Modelling of Atomic-Scale Defect Phenomena in Compound Semiconductors R.M. Nieminen, T. Mattila, and S. Poykko ....................................... 11

The Generalized-Gradient Approximation to Density Functional Theory and Bonding D.C. Patton, M. Pederson, and D.V. Porezag .................................... 37

Electronic Structure Calculations and Molecular Dynamics Using the Real-Space Method and Optimized Ultra-soft Pseudopotential T. Hoshi and T. Fujiwara ................................................................... 51

Quantum Simulations Using Linear Scaling Methods: Clusters on Surfaces G. Galli, A. Canning, and F. Mauri ................................................... 59

Electronic Structure of Disordered Alloys R. Prasad ............................................................................................ 65

Computer Simulation of Structure and Dynamics in Complex Materials S.L. Chaplot ....................................................................................... 89

IX

Part III Alloys

First-Principles Thermodynamics of Alloys J .M. Sanchez ..................................................................................... 101

Electronic Structure of Binary Systems G.P. Das ............................................................................................ 108

First-Principles Phase Stability Study of Metallic Alloys P.P. Singh .......................................................................................... 121

First-Principles Approach to Ordering and Clustering Behavior in Metallic Alloys: Application to AI-Li and Ni-Mo Systems A. Arya, S. Banerjee, and G.P. Das .................................................. 127

Thermochemical Modeling of Temary Alloys from Binary Systems R. Ganesan and S. Vana Varamban .................................................. 137

Superconductivity in Zr2Rh and its Hydrides: Theory and Experiment H.G. Salunke, G.P. Das, V.C. Sahni, and P. Raj .............................. 142

Part IV Correlated Electron Systems

Ab-initio Approach to Electronic Excitation Spectra in Perovskite LaM03 Oxides D.D. Sarma and P. Mahadevan ......................................................... 149

Theory for the Interdependence of High-Tc Superconductivity and Dynamic Spin Fluctuations S. Grabowski, J. Schmalian, M. Langer, and K.H. Bennemann . ..... ................... ............ ......... ..... .... ........... ...... 162

Electrical Resistivity and Positron Lifetime Studies in the Kondo Insulating System, FeSit_xGex A. Bharathi, Y. Hariharan, A. Mani, and C.S. Sundar ..................... 170

x

Part V Clusters and Nanomaterials

Electronic Structure of Magic Metal Clusters and Cluster Assemblies P. Jena, S.N. Khanna, and B.K. Rao ................................................ 179

Stability of Molecules and Clusters Studied Through First-Principles Total Energy Calculations S. Mukherjee, AP. Seitsonen, and RM. Nieminen ......................... 187

Adsorption on Clusters Vijay Kumar .. ........................ ....... ...................... ................ .............. 193

Ab-initio Molecular Dynamics Study of Impurity in Metal Clusters: NanAI (n = 1-10) D.G. Kanhere, A Dhavale, and V. Shah .......................................... 202

Lyapunov Exponent at the Melting Transition in Small Ni Clusters V. Mehra and R. Ramaswamy ......................................................... 209

Monte Carlo Studies of Argon Clusters Confined in Zeolites R Chitra and S. Yashonath ..................................................... ;........ 214

Structure-Property Relation in Oxide Nanopartic1es P. Ayyub ............................................................................. .............. 228

Nanopartic1es of II-VI Semiconductors S.K. Kulkarni, M. Kundu, and P. Borse ........................................... 236

Cu Doped ZnO Quantum Dots: Intrinsic and Extrinsic Luminescence S. Mahamuni, K. Borgohain, B.S. Bendre, and S.S. Joshi ................ 244

Carrier Dynamics in Porous and Nanocrystalline Silicon V.A. Singh and G.C. John ................................................................. 250

Anodisation Time Dependence of Photoluminiscence Properties of Porous Silicon R Rajaraman, P. Gopalan, B.S. Panigrahi, and M. Premila.............. 257

XI

Formation ofNanocrystalline Fe-Cu-Nb-Si-B Alloys N. Bhagat, Ajay Gupta, and P. Duhaj ................................................ 261

Magnetic Properties of Ultra-fine 'Y' - Fe4N R.N. Panda and N.S. Gajbhiye .......................................................... 265

Part VI Surfaces and Interfaces

First-Principles Calculation of Surface Step Energies and Interactions J. F. Annett ........................................................................................ 271

Deposition ofGa and As Adatoms on the Ge(!!!) and Si(11!) Surfaces: A First-Principles Study C. Cheng and K. Kunc '" ......... .............. .............. ......... ....... ... ........... 279

Steering and Isotope Effects in the Dissociative Adsorbtion of H2/Pd(1 00) A. Gross and M. Scheffler ....... ......... ....... ...... ......... ....... .................... 285

Growth and Magnetism of Rough Transition Metal Overlayers A. Mookerjee ............ ............... ...................... ....... ..... ......... .... ........... 293

Quantum Adsorbates: Helium in Zeolites C. Chakravarty and K.V. Thiruvengadaravi ...................................... 305

Effect of High-Energy Heavy-Ion Irradiation on FeiTh Multilayers A. Paul, A. Gupta, R. Gupta, D.K. Avasthi, and G. Principi ............ 309

Part VII Phase Transitions

Isostructural Solid-Solid Transition in Crystalline Systems with Short Ranged Interaction P. Bolhuis and D. Frenkel ................................................................. 315

Quantum Effects and Phase Transitions in Adsorbed Molecular Layers P. Nielaba ............ ...... ............... ...................................... ................... 325

XII

Anchoring Transitions of Nematic Liquid Crystals Induced by Solid Substrate 1. Chakrabarti and B. Mulder ............................................................ 334

Monte Carlo Simulation of the Kinetics of Martensitic-type Restacking Transitions: Dynamic Scaling and Universal Growth Exponents S.P. Shrestha and D. Pandey............................................................. 339

Structural Transitions of a Soft Solid: The Skyrmion Lattice M. Rao, S. Sengupta, and R. Shankar ............................................... 348

Electronic Topological Transitions in Elemental Metals and Compounds B.K. Godwal, R.S. Rao, and S.K. Sikka ........................................... 356

Role of High Pressure in Designing Novel Phases P.Ch. Sahu, K. Govinda Rajan, N.V. Chandra Shekar, and M. yousuf.............. ...................... .................................... ........... 365

Pressure-Induced Polymerisation of Fullerenes C.S. Sundar, M. Premila, P.Ch. Sahu, A. Bharathi, Y. Hariharan, D.V.S. Muthu, and A.K. Sood .......................................................... 376

Part VIII Microstructure and Deformation

Microstructural Evolution During Precipitation in Stressed Solids T.A. Abinandanan and R. Sankarasubramanian ............................... 387

Modelling of Process for Controlled Microstructure of Material P.V. Sivaprasad ................................................................................. 395

Multiscaling in Normal Grain Growth: A Monte Carlo Study S. Koka, P.V. Sivaprasad, V. Sridhar, S. Venkadesan, and K.P.N. Murthy ............................................................................ 404

Non-destructive Evaluation of Defects: A Model-Based Approach B. Raj, P. Kalyanasundaram, R. Sivaramanivas, and C. Babu Rao ................................................................................ 410

XIII

Deformation ofNanostructured Materials K.A. Padmanabhan ........... ....................... .... .................... ........... ....... 418

Mechanics of Powder Compaction Ch. PavanaChand and R. KrishnaKumar ......... ...... ...... ..... ................ 426

Finite Element Modelling of the Creep Behaviour ofWeldments A.K. Bhaduri ....... .................................. ......... .... .................... ........... 434

List of Authors ......................................... .... ....... ...... .......... ... ...... 445

XIV