This book highlights the intrinsic structures of all kinds of energetic compounds and some structure–property relationships therein. Energetic materials are a class of energy materials that can transiently release a large amount of gases and heat by self-redox after stimulated and usually refer to explosives, propellants and pyrotechnics. Nowadays, in combination with various theories and simulation-aided material design technologies, many new kinds of energetic materials like energetic extended solids, energetic ionic salts, energetic metal organic frames, energetic co-crystals and energetic perovskites have been created, in addition to traditional energetic molecular crystals. It is somewhat dazzling, and an issue of how we can understand these new types of energetic materials is raised. In the past about 20 years, we were immersed in the computational energetic materials. By means of defining a concept of intrinsic structures of energetic materials, which refers to the crystal packing structure of energetic materials, as well as molecule for molecular solid specially, the microscopic structures have been mostly clarified, and related with many macroscopic properties and performances, with molecular simulations. This book presents our understanding about it. Thereby, a simply and new way to readily understand energetic materials is expected to be paved, based on this book.
It contains energetic molecular crystals, energetic ionic crystals, energetic atomic crystals, energetic metallic crystals and energetic mixed-type crystals and the substructures closest to crystal packing. Meanwhile, the common intermolecular interactions in energetic crystals will be introduced. In addition, theoretical and simulation methods for treating the intrinsic structures will be briefed, as they are the main tools to reveal the molecules and crystals. Besides, the polymorphism as a level of intrinsic structures will be briefly discussed. In the final of this book, we introduce the crystal engineering of energetic materials. This book features the first proposal of intrinsic structure and crystal engineering of energetic materials and the understanding of the properties and performances of energetic materials by maintaining a concept that structure determines property. It helps to promote the rationality in creating new energetic materials, rather than increase experience.
Author(s): Chaoyang Zhang, Jing Huang, Rupeng Bu
Publisher: Springer-Science Press
Year: 2023
Language: English
Pages: 468
City: Beijing
Preface
Introduction
Contents
About the Authors
1 Overview
1.1 Energetic Materials
1.2 Intrinsic Structures of Energetic Materials
1.3 Benefits of the Introduction of Intrinsic Structures
1.4 Intention and Organization of This Book
References
2 Category of Energetic Crystals
2.1 Introduction
2.2 Criterion for Categorizing Energetic Crystals
2.2.1 Primary Constituent Part
2.2.2 Type of Energetic Crystals
2.3 Category of Energetic Crystals
2.3.1 Energetic Molecular Crystal
2.3.2 Energetic Ionic Crystal
2.3.3 Energetic Atomic Crystal
2.3.4 Energetic Metallic Crystal
2.3.5 Energetic Mixed-Type Crystal
2.4 Understanding of Energetic Crystals
2.4.1 Interactions Between PCPs in Crystals and Their Stability
2.4.2 Energy Content
2.5 Conclusions and Outlooks
References
3 Application of Molecular Simulation Methods in Treating Intrinsic Structures of Energetic Materials
3.1 Introduction
3.1.1 Weight of Simulation in Energetic Material Researches
3.1.2 Importance of Molecular Simulation
3.2 Quantum Chemical Methods for Treating Energetic Molecules
3.2.1 Quantum Chemical Methods
3.2.2 Description for Geometric Structure
3.2.3 Description for Electronic Structure
3.2.4 Description for Energetics
3.2.5 Description for Reactivity
3.3 Dispersion-Corrected DFT Methods and Their Application
3.3.1 Reliability to Density Prediction
3.3.2 Reliability to Geometric Prediction
3.3.3 Reliability to Lattice Energy Prediction
3.3.4 Comparison of Computation Efficiency
3.4 Molecular FF Methods and Their Application
3.4.1 Classic FFs and Their Application
3.4.2 Consistent FFs and Their Application
3.4.3 Reactive Forcefield and Its Application
3.5 Hirshfeld Surface Analysis Method
3.5.1 Principle
3.5.2 Description for Intermolecular Interaction
3.5.3 Description for a Same Molecule in Various Crystal Environments
3.5.4 Description for a Same Ion in Various Crystal Environments
3.5.5 Predictions for Shear Sliding Characteristic and Impact Sensitivity
3.5.6 Summary of Advantages and Disadvantages
3.6 Codes and Database Applied for Energetic Molecules and Crystals
3.6.1 Gaussian
3.6.2 Multiwfn
3.6.3 VASP
3.6.4 Materials Studio
3.6.5 DFTB+
3.6.6 CP2K
3.6.7 LAMMPS
3.6.8 COSMOlogic
3.6.9 CrystalExplorer
3.6.10 CSD
3.7 Conclusion and Outlooks
References
4 Energetic Molecules and Energetic Single-Component Molecular Crystals
4.1 Introduction
4.2 Traditional Energetic Molecular Crystals
4.2.1 Energetic Nitro Compounds
4.2.2 Energetic Conjugated N-heterocyclic Compounds
4.2.3 Energetic Organic Azides
4.2.4 Energetic Compounds with Different Heat Resistance
4.2.5 Energetic Compounds with Different Impact Sensitivity
4.3 Energetic Halogen Compounds
4.3.1 Energetic Fluorine Compounds
4.3.2 Energetic compounds with Chlorine, Bromine, or Iodine
4.4 Entropy Explosives: Energetic Peroxides
4.4.1 Energetic Peroxides
4.4.2 Introduction of Entropic Explosion
4.5 Full Nitrogen Molecules
4.6 Conclusions and Outlooks
References
5 Polymorphism and Polymorphic Transition in Energetic Molecular Crystals
5.1 Introduction
5.2 Polymorphism and Polymorphic Transition
5.2.1 Polymorphism
5.2.2 Polymorphic Transition
5.3 Factors Influencing the Polymorphic Transition
5.3.1 Crystal Quality
5.3.2 Additive
5.4 Polymorph-Reduced Differences in Structure and Energetics
5.4.1 Molecular Structure
5.4.2 Molecular Packing
5.4.3 Morphology
5.4.4 Energetics
5.4.5 Detonation Property
5.5 Polymorph-Dependent Mechanism of Thermal Decomposition
5.5.1 Mechanism of Thermal Decomposition of CL-20 Polymorphs
5.5.2 Mechanism of Thermal Decomposition of HMX Polymorphs
5.6 Polymorph Transition-Induced Low Impact Sensitivity of FOX-7
5.6.1 Stacking Structures of FOX-7 Polymorphs
5.6.2 Sliding Characteristics of FOX-7 Polymorphs
5.6.3 Correlation Between the Low Impact Sensitivity of FOX-7 and Its Heat-Induced Polymorphic Transition
5.7 Strategies for Controlling Polymorphic Transition
5.7.1 Recrystallization
5.7.2 Coating Crystal
5.7.3 Adding Additive
5.8 Conclusions and Outlooks
References
6 Energetic Ionic Crystals
6.1 Introduction
6.2 Composition and Category
6.2.1 Composition of Energetic Ionic Crystals
6.2.2 Category of Energetic Ionic Crystals
6.3 Volumetric and Electric Variabilities of Constituent Ions
6.3.1 Volumetric Variability
6.3.2 Electric Variability
6.4 Packing Structure and Intermolecular HB
6.4.1 Packing Structure
6.4.2 Intermolecular HB
6.4.3 Consequence of Strengthened HB
6.5 Energetic Inorganic Ionic Crystals
6.6 Energetic Organic Ionic Crystals
6.6.1 Ionic Crystals Containing Tetrazole Derivative
6.6.2 Ionic Crystals Containing Triazole Derivative
6.6.3 Other Energetic Organic Ionic Crystals
6.7 Conclusions and Outlook
References
7 Energetic Cocrystals
7.1 Introduction
7.2 Redefinition and Intension of the Term Cocrystal
7.2.1 Insufficiency of the Existent Definitions and Classifications
7.2.2 History of Cocrystal and Its Relatives
7.2.3 Redefinition of Cocrystal with a Broader Intension
7.3 Component, Intermolecular Interaction, and Packing Structure of Energetic Cocrystal
7.3.1 CL-20-Based Cocrystals
7.3.2 HMX-Based Cocrystals
7.3.3 EDNA, BTATz, DNPP, aTRz, BTNMBT, and BTO-Based Cocrystals
7.3.4 TNT, DNBT, DNAN, and HNS-Based Energetic Cocrystals
7.3.5 BTF-Based Energetic Cocrystals
7.3.6 TXTNB-Based Cocrystals
7.3.7 Heterocycle Molecules-Based Cocrystals
7.4 Thermodynamics for the Formation of Energetic Cocrystal
7.4.1 Calculation Methods
7.4.2 Thermodynamic Parameters
7.5 Property and Performance of Energetic Cocrystal
7.5.1 Density, and Detonation Velocity and Pressure
7.5.2 Thermal Stability and Impact Sensitivity
7.5.3 Reactivity: A Case of CL-20/HMX
7.6 Conclusions and Outlooks
References
8 Energetic Atomic Crystals, Energetic Metallic Crystals, and Energetic Mixed-Type Crystals
8.1 Introduction
8.2 Energetic Atomic Crystals
8.2.1 Polymeric Nitrogen
8.2.2 Polymeric CO and CO2
8.3 Energetic Metallic Crystals
8.3.1 Metallic Hydrogen
8.3.2 Metallic Nitrogen
8.4 Energetic Mixed-Type Crystals
8.4.1 Energetic Perovskites
8.4.2 N5−-based Mixed-Type Crystals
8.4.3 Other Mixed-Type Cocrystals
8.5 Conclusion and Outlooks
References
9 Hydrogen Bonding, Hydrogen Transfer, and Halogen Bonding
9.1 Introduction
9.2 Hydrogen Bonding
9.2.1 Hydrogen Bonding in Energetic Homogeneous Molecular Crystals
9.2.2 Hydrogen Bonding in Energetic Cocrystals
9.2.3 Hydrogen Bonding in Energetic Ionic Compounds
9.3 Effects of Hydrogen Bonding in Energetic Compounds
9.3.1 On Crystal Packing
9.3.2 On Impact Sensitivity
9.4 Hydrogen Transfer
9.4.1 Intramolecular H-transfer
9.4.2 Hydrogen Transfer in Crystal
9.5 Effect of H-transfer
9.5.1 On Thermal Stability
9.5.2 On Impact Sensitivity
9.6 Halogen Bonding in Energetic Compounds
9.7 Conclusions and Outlooks
References
10 π-Stacking in Energetic Crystals
10.1 Introduction
10.2 π-π Stacking
10.2.1 Energetic Planar π-Bonded Molecules
10.2.2 HB-Aided π-π Stacking
10.2.3 Non-HB-Aided π-π Stacking
10.2.4 Heat/pressure Induced Variation of π-π Stacking
10.3 n-π Stacking
10.3.1 Intension of n-π Stacking
10.3.2 n-π Stacking Structures
10.3.3 Nature of n-π Stacking: Electrostatic Interaction
10.4 Comparison Among n-π Stacking, π-π Stacking, and Intermolecular HB
10.5 Molecular Structure-Stacking Mode Relationship: A Case of D2h and D3h Molecules
10.5.1 Data Collection and Verification of Molecular Stacking Pattern
10.5.2 Molecular Structures and Stacking Patterns
10.5.3 Intralayered Intermolecular Interactions
10.5.4 Characteristics of D2h and D3h Molecules Stacked in the Planar-Layer Mode
10.6 Conclusions and Outlooks
References
11 Crystal Engineering for Creating Low Sensitivity and High Energy Materials
11.1 Introduction
11.2 Energy-Safety Contradiction of Energetic Materials
11.3 Crystal Packing-Impact Sensitivity Relationship of Energetic Materials
11.4 Strategy to Achieve High Packing Density
11.4.1 Crystal Structural Data Collection
11.4.2 dm-PC Contradiction of High Density Energetic Compounds
11.4.3 Influences of Molecular Composition and Intermolecular Interaction on Density
11.4.4 Strategy for Increasing dc
11.5 Strategy for Creating LSHEMs
11.5.1 Strategy for Creating Traditional Low Sensitivity Energetic Materials
11.5.2 Strategy for Creating Low Sensitive or Desensitized Energetic Cocrystals
11.5.3 Strategy for Creating Low Sensitive or Desensitized Energetic Ionic Compounds
11.6 Conclusions and Outlook
References
Appendix A Symbols and Meaning
Appendix B Abbreviations of Molecules
Appendix C Crystal Codes and Full Names
