Atomistic Simulations of Glasses

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