A complete reference to computer simulations of inorganic glass materials
In Atomistic Simulations of Glasses: Fundamentals and Applications, a team of distinguished researchers and active practitioners delivers a comprehensive review of the fundamentals and practical applications of atomistic simulations of inorganic glasses. The book offers concise discussions of classical, first principles, Monte Carlo, and other simulation methods, together with structural analysis techniques and property calculation methods for the models of glass generated from these atomistic simulations, before moving on to practical examples of the application of atomistic simulations in the research of several glass systems.
The authors describe simulations of silica, silicate, aluminosilicate, borosilicate, phosphate, halide and oxyhalide glasses with up-to-date information and explore the challenges faced by researchers when dealing with these systems. Both classical and ab initio methods are examined and comparison with experimental structural and property data provided. Simulations of glass surfaces and surface-water reactions are also covered.
Atomistic Simulations of Glasses includes multiple case studies and addresses a variety of applications of simulation, from elucidating the structure and properties of glasses for optical, electronic, architecture applications to high technology fields such as flat panel displays, nuclear waste disposal, and biomedicine. The book also includes:
- A thorough introduction to the fundamentals of atomistic simulations, including classical, ab initio, Reverse Monte Carlo simulation and topological constraint theory methods
- Important ingredients for simulations such as interatomic potential development, structural analysis methods, and property calculations are covered
- Comprehensive explorations of the applications of atomistic simulations in glass research, including the history of atomistic simulations of glasses
- Practical discussions of rare earth and transition metal-containing glasses, as well as halide and oxyhalide glasses
- In-depth examinations of glass surfaces and silicate glass-water interactions
Perfect for glass, ceramic, and materials scientists and engineers, as well as physical, inorganic, and computational chemists, Atomistic Simulations of Glasses: Fundamentals and Applications is also an ideal resource for condensed matter and solid-state physicists, mechanical and civil engineers, and those working with bioactive glasses. Graduate students, postdocs, senior undergraduate students, and others who intend to enter the field of simulations of glasses would also find the book highly valuable.
Table of Contents
Preface
Part I Fundamentals of Atomistic Simulations
Chapter 1 Classical simulation methods
Abstract
1.1 Introduction
1.2 Simulation techniques
1.2.1 Molecular dynamics (MD)
1.2.1.1 Integrating the equations of motion
1.2.1.2 Thermostats and barostats
1.2.2 Monte Carlo (MC) eimulations
1.2.2.1 Kinetic Monte Carlo
1.2.2.2 Reverse Monte Carlo
1.3 The Born Model
1.3.1 Ewald summation
1.3.2 Potentials
1.3.2.1 Transferability of potential parameters: Self-consistent sets
1.3.2.2 Ion polarizability
1.3.2.3 Potential models for borates
1.3.2.4 Modelling reactivity: electron transfer
1.4 Calculation of Observables
1.4.1 Atomic structure
1.4.2 Hyperdynamics and peridynamics
1.5 Glass Formation
1.5.1 Bulk structures
1.5.2 Surfaces and fibers
1.6 Geometry optimization and property calculations
1.7 References
Chapter 2 Ab initio simulation of amorphous solids
Abstract
2.1 Introduction
2.1.1 Big picture
2.1.2 The limits of experiment
2.1.3 Synergy between experiment and modeling
2.1.4 History of simulations and the need for ab initio methods
2.1.5 The difference between ab initio and classical MD
2.1.6 Ingredients of DFT
2.1.7 What DFT can provide
2.1.8 The emerging solution for large systems and long times: Machine Learning
2.1.9 A practical aid: Databases
2.2 Methods to produce models
2.2.1 Simulation Paradigm: Melt Quench
2.2.2 Information Paradigm
2.2.3 Teaching chemistry to RMC: FEAR
2.2.4 Gap Sculpting
2.3 Analyzing the models
2.3.1 Structure
2.3.2 Electronic Structure
2.3.3 Vibrational Properties
2.4 Conclusion
2.5 Acknowledgements
2.6 References
Chapter 3 Reverse Monte Carlo simulations of non-crystalline solids
Abstract
3.1 Introduction -- why RMC is needed?
3.2 Reverse Monte Carlo modeling
3.2.1. Basic RMC algorithm
3.2.2. Information deficiency
3.2.3. Preparation of reference structures: hard sphere Monte Carlo
3.2.4. Other methods for preparing suitable structural models
3.3 Topological analyses
3.3.1. Ring statistics
3.3.2. Cavity analyses
3.3.3. Persistent homology analyses
3.4 Applications
3.4.1 Single component liquid and amorphous materials
3.4.1.1 l-Si and a-Si
3.4.1.2 l-P under high pressure and high temperature
3.4.2 Oxide glasses
3.4.2.1 SiO2 glass
3.4.2.2 R2O-SiO2 glasses (R=Na, K)
3.4.2.3 CaO-Al2O3 glass
3.4.3 Chalcogenide glasses
3.4.4 Metallic glasses
3.5 Summary
3.6 Acknowledgments
3.7 References
Chapter 4 Structure analysis and property calculations
abstract
4.1 Introduction
4.2 Structure Analysis
4.2.1 Salient features of glass structures
4.2.2 Classification of the range order.
4.3 Real Space Correlation functions.Spectroscopic properties: validating the structural models
4.3.1 X-ray and Neutron diffraction spectra
4.3.2 Vibrational spectra
4.3.3 NMR spectra
4.4 Transport properties
4.4.1 Diffusion coefficient and diffusion activation energy
4.4.2 Viscosity
4.4.3 Thermal conductivity
4.5 Mechanical Properties
4.5.1 Elastic constants
4.5.2 Stress-strain diagrams and fracture mechanism
4.6 Concluding remarks
4.7 References
Chapter 5 Topological constraint theory of glass: counting constraints by molecular dynamics simulations
Abstract
5.1 Introduction
5.2 Background and topological constraint theory
5.2.1 Rigidity of mechanical networks
5.2.2 Application to atomic networks
5.2.3 Constraint enumeration under mean-field approximation
5.2.4 Polytope-based description of glass rigidity
5.2.5 Impact of temperature
5.2.6 Need for molecular dynamics simulations
5.3 Counting constraints from molecular dynamics simulations
5.3.1 Constraint enumeration based on the relative motion between atoms
5.3.2 Computation of the internal stress
5.3.3 Computation of the floppy modes
5.3.5 Dynamical matrix analysis
5.4 Conclusions
5.5 References
Part II Applications of Atomistic Simulations in Glass Research
Chapter 6 History of atomistic simulations of glasses
Abstract
6.1 Introduction
6.2 Simulation techniques
6.2.1 Monte Carlo techniques
6.2.2 Molecular dynamics
6.3 Classical simulations: interatomic potentials
6.3.1 Potential models for silica
6.3.1.1 Silica: quantum mechanical simulations
6.3.2 Modified silicates and aluminosilicates
6.3.3 Borate glasses
6.3.3.1 Borates: quantum mechanical simulations
6.4 Simulation of surfaces
6.5 Computer science and engineering
6.6.1 Software
6.6.2 Hardware
6.6 References
Chapter 7 Silica and silicate glasses
Abstract
7.1 Introduction
7.2 Atomistic simulations of silicate glasses: ingredients and critical aspects
7.3 Characterization and experimental validation of structural and dynamic features of simulated glasses
7.3.1 Structural characterizations
7.3.2 Dynamic properties of simulated glasses
7.3.3 Validation and experimental confirmation of structural and dynamic properties
7.3.3.1 Diffraction methods
7.3.3.2 Nuclear Magnetic Resonance
7.3.3.3 Vibrational spectral characterization
7.4 MD simulations of silica glasses
7.5 MD simulations of alkali silicate and alkali earth silicate glasses
7.5.1 Local environments and distribution of alkali ions
7.5.2 The mixed alkali effect
7.6 MD simulations of aluminosilicate glasses
7.7 MD simulations of nanoporous silica and silicate glasses
7.8 AIMD simulations of silica and silicate glasses
7.9 Summary and Outlook
Acknowledgements
References
Chapter 8 Borosilicate and boroaluminosilicate glasses
8.1 Abstract
8.2 Introduction
8.3 Experimental determination and theoretical models of boron N4 values in borosilicate glass
8.3.1 Experimental results on boron coordination number
8.3.2 Theoretical models in predicting boron N4 value
8.4 ab initio versus classical MD simulations of borosilicate glasses
8.5 Empirical potentials for borate and borosilicate glasses
8.5.1 Recent development of rigid ion potentials for borosilicate glasses
8.5.2 Development of polarizable potentials for borate and borosilicate glasses
8.6 Evaluation of the potentials
8.7 Effects of cooling rate and system size on simulated borosilicate glass structures
8.8 Applications of MD simulations of borosilicate glasses
8.8.1 Borosilicate glass
8.8.2 Boroaluminosilicate glasses
8.8.3 Boron oxide-containing multi-component glass
8.9 Conclusions
8.10 Appendix: Available empirical potentials for boron-containing systems
8.10.1 Borosilicate and boroaluminosilicate potentials-Kieu et al and Deng&Du
8.10.2 Borosilicate potential- Wang et al
8.10.3 Borosilicate potential-Inoue et al
8.10.4 Boroaluminosilicate potential-Ha and Garofalini
8.10.5 Borosilicate and boron-containing oxide glass potential-Deng and Du
8.10.6 Borate, boroaluminate and borosilicate potential-Sundararaman et al
8.10.7 Borate and borosilicate polarizable potential-Yu et al
8.10 Acknowledgements
8.11 References
Chapter 9 Nuclear waste glasses
9.1 Preamble
9.2 Introduction to French nuclear glass
9.2.1 Chemical composition
9.2.2 About the long term behavior (irradiation, glass alteration, He accumulation)
9.2.3 What can atomistic simulations contribute?
9.3 Computational methodology
9.3.1 Review of existing classical potentials for borosilicate glasses
9.3.2 Preparation of a glass
9.3.3 Displacement cascade simulations
9.3.4 Short bibliography about simplified nuclear glass structure studies
9.4 Simulation of radiation effects in simplified nuclear glasses
9.4.1 Accumulation of displacement cascades and the thermal quench model
9.4.2 Preparation of disordered and depolymerized glasses
9.4.3 Origin of the hardness change under irradiation
9.4.4 Origin of the fracture toughness change under irradiation
9.5 Simulation of glass alteration by water
9.5.1 Contribution from ab initio calculations
9.5.2 Contribution from Monte Carlo simulations
9.6 Gas incorporation: radiation effects on He solubility
9.6.1 Solubility model
9.6.2 Interstitial sites in SiO2-B2O3-Na2O glasses
9.6.3 Discussion about He solubility in relation to the radiation effects
9.7 Conclusions
9.8 Acknowledgements
9.9 References
Chapter 10 Phosphate glasses
Abstract
10.1 Introduction to phosphate glasses
10.1.1 Applications of phosphate glasses
10.1.2 Synthesis of phosphate glasses
10.1.3 The modified random network model applied to phosphate glasses
10.1.4 The tetrahedral phosphate glass network
10.1.5 Modifier cations in phosphate glasses
10.2 Modelling methods for phosphate glasses
10.2.1 Configurations of atomic coordinates
10.2.2 Molecular modelling versus reverse Monte Carlo modelling
10.2.3 Classical vs. ab initio molecular modelling
10.2.4 Evaluating the simulation of interatomic interactions
10.2.5 Evaluating models of glasses by comparison with experimental data
10.3 Modelling pure vitreous P2O5
10.3.1 Modelling of crystalline P2O5
10.3.2 Modelling of vitreous P2O5
10.3.3 Cluster models of vitreous P2O5
10.4 Modelling phosphate glasses with monovalent cations
10.4.1 Modelling lithium phosphate glasses
10.4.2 Modelling sodium phosphate glasses
10.4.3 Modelling phosphate glasses with other monovalent cations
10.4.4 Modelling phosphate glasses with monovalent cations and addition of halides
10.4.5 Cluster models of alkali phosphate glasses
10.5 Modelling phosphate glasses with divalent cations
10.5.1 Modelling zinc phosphate glasses
10.5.2 Modelling zinc phosphate glasses with additional cations
10.5.3 Modelling alkaline earth phosphate glasses
10.5.4 Modelling lead phosphate glasses
10.6 Modelling phosphate based glasses for biomaterials applications
10.6.1 Modelling Na2O-CaO-P2O5 glasses with 45 mol% P2O5
10.6.2 Modelling Na2O-CaO-P2O5 glasses with 50 mol% P2O5
10.6.3 Modelling Na2O-CaO-P2O5 glasses with additional cations
10.7 Modelling phosphate glasses with trivalent cations
10.7.1 Modelling iron phosphate glasses
10.7.2 Cluster models of iron phosphate glasses
10.7.3 Modelling trivalent rare earth phosphate glasses
10.7.4 Modelling aluminophosphate glasses
10.8 Modelling phosphate glasses with tetravalent and pentavalent cations
10.9 Modelling phosphate glasses with mixed network formers
10.9.1 Modelling borophosphate glasses
10.9.2 Modelling phosphosilicate glasses
10.10 Modelling bioglass 45S and related glasses
10.10.1 Modelling bioglass 45S and related glasses from the same system
10.10.2 Modelling bioglass 45S and related glasses with additional components
10.11 Summary
10.12 References
Chapter 11 Bioactive glasses
Abstract
11.1 Introduction
11.2 Methodology
11.3 Development of interatomic potentials
11.4 Structure of 45S5 Bioglass
11.5 Inclusion of ions into bioactive glass and the effect on structure and bioactivity
11.6 Glass nanoparticles and surfaces
11.7 Discussion and future work
Bibliography
Chapter 12 Rare earth and transition metal containing glasses
Abstract
12.1 Introduction
12.1.1 Transition metal and rare earth oxides in glasses: importance and potential applications
12.1.2 Effects of local structures and clustering behaviors of RE and TM ions on properties
12.1.3 Redox reaction and multioxidation states of TM and RE ions
12.1.4 Effect of composition on multioxidation states in glasses containing TM
12.1.5 The role of MD in investigating TM and RE containing glasses
12.2 Simulation methodologies
12.2.1 Interatomic potentials and glass simulations
12.2.2 Cation environment and clustering analysis
12.2.3 Diffusion and dynamic property calculations
12.2.4 Electronic structure calculations
12.3 Case studies of MD simulations of RE and TM containing glasses
12.3.1 Rare earth doped silicate and aluminophosphate glasses for optical applications
12.3.1.1 Erbium doped silica and silicate glasses: from melt-quench to ion implantation
12.3.1.2 Europium and praseodymium doped silicate glasses
12.3.1.3 Cerium doped aluminophosphate glasses: atomic structure and charge trapping
12.3.2 Alkali vanadophosphate glasses as a mixed conductor
12.3.2.1 General features of vanadophosphate glasses
12.3.2.2 Sodium vanadophosphate glass
12.3.2.3 Lithium vanadophosphate glass
12.3.3 Zirconia containing aluminosilicate and borosilicate glasses for nuclear waste disposal
12.4 Conclusions
Acknowledgement
References
Chapter 13 Halide and oxyhalide glasses
Abstract
13.1 Introduction
13.2 General Structure Features of Fluoride and Oxyfluoride Glasses
13.2.1 Structure Features of Fluoride Glasses
13.2.2 Structure Features of Oxyfluoride Glasses
13.2.3 Phase Separation in Fluoride and Oxyfluoride Glasses
13.3 Structures and Properties of Fluoride Glasses from MD Simulations
13.3.1 General Structures from MD simulations
13.3.2 Cation Coordination and Structural Roles
13.3.3 Fluorine Environments
13.4 MD Simulations of Fluoroaluminosilicate Oxyfluoride Glasses
13.4.1 Oxide and Fluoride Glass Phase Separation Observed from MD Simulations
13.4.2 Oxide-Fluoride Interfacial Structure Features from MD simulations
13.4.3 Correlation of Structural Features between MD and Crystallization
13.5 ab initio MD simulations of oxyfluoride glasses
13.6 Conclusions
Acknowledgements
References
Chapter 14 Glass surface simulations
abstract
14.1 Introduction
14.2 Classical molecular dynamics surface simulations
14.2.1 amorphous silica surfaces
14.2.2 Multicomponent oxide glass surfaces
14.2.2.1 Bioactive glasses
14.2.3 Wet glass surfaces
14.2.3.1 Reactive potentials
14.3 First Principles Surface Simulations
14.3.1 Silica glass surfaces
14.3.2 Multicomponent glass surfaces
14.3.3 Wet glass surfaces
14.4 Summary
Acknowledgements
References
Chapter 15 Simulations of glass - water interactions
Abstract
15.1 Introduction
15.1.1 Glass Dissolution Process and Experimental Characterizations
15.1.2 Types of Atomistic Simulation Methods for Studying Glass-Water Interactions
15.2 First-Principles Simulations of Glass-Water Interactions
15.2.1 Brief Introduction to Methods
15.2.2 Energy Barriers for Si-O-Si Bond Breakage
15.2.3 Reaction Mechanism for Si-O-Si Bond Breakage
15.2.4 Strained Si-O-Si linkages
15.2.5 Reaction Energies for Multicomponent Linkages
15.2.6 Effect of pH on Si-O-Si Hydrolysis Reactions
15.2.7 Nanoconfinement of water in porous materials
15.2.8 Oniom or QM/MM simulations
15.2.9 Areas for improvement/additional research
15.3 Classical Molecular Dynamics Simulations of water-glass interactions
15.3.1 Brief Introduction and History
15.3.2 Non-Reactive Potentials
15.3.3 Reactive Potentials
15.3.4 Silica Glass-Water Interactions
15.3.5 Silicate Glass - Water Interactions
15.3.6 Other glasses - water interactions
15.3.7 Areas for Improvement
15.4 Challenges and Outlook
15.4.1 Extending the Length and Time Scales of Atomistic Simulation
15.4.2 Reactive Potential Development
15.5 Conclusion Remarks
15.6 Acknowledgements
15.7 References
