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Theoretical and Computational Approaches to Predicting Ionic Liquid Properties - 1st Edition - ISBN: 9780128202807

Theoretical and Computational Approaches to Predicting Ionic Liquid Properties

1st Edition

Editors: Aswathy Joseph Suresh Mathew
Paperback ISBN: 9780128202807
Imprint: Elsevier
Published Date: 1st November 2020
Page Count: 200
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Theoretical and Computational Approaches to Predicting Ionic Liquid Properties highlights new approaches to predicting and understanding ionic liquid behavior and selecting ionic liquids based on theoretical knowledge corroborated by experimental studies. Supported throughout with case studies, the book provides a comparison of the accuracy and efficiency of different theoretical approaches. Sections cover the need for integrating theoretical research with experimental data, conformations, electronic structure and non-covalent interactions, microstructures and template effects, thermodynamics and transport properties, and spectro-chemical characteristics. Catalytic and electrochemical properties are then explored, followed by interfacial properties and solvation dynamics.

Structured for ease of use, and combining the research knowledge of a global team of experts in the field, this book is an indispensable tool for those involved with the research, development and application of ionic liquids across a vast range of fields.

Key Features

  • Highlights new approaches for selecting ionic liquids by combining theoretical knowledge with experimental and simulation-based observations
  • Discusses how theoretical simulation can help in selecting specific anion-cation combinations to show enhanced properties of interest
  • Compares the accuracy and efficiency of different theoretical approaches for predicting ionic and liquid characteristics


Chemists across a range of fields involved with the theoretical investigation and application of ionic liquids, in particular theoretical, organic, green and materials chemists. In addition, all those who employ ionic liquids in their work, including chemical engineers, materials scientists, pharmaceutical scientists, engineers, and environmental scientists across both academia and industry

Table of Contents

1. Introduction and Overview of Theoretical and Computational Approaches to Predicting Ionic Liquid Properties
1.1. Introduction
1.2. Ionic Liquids
1.3. Computing Molecular Properties of Ionic Liquids
1.4. Necessity for Integrating Experiment and Theoretical Research
1.5. Scope of the Book
1.6. Theoretical Approaches
1.6.1. Molecular Mechanics
1.6.2.Semi-Empirical methods
1.6.3. Ab initio Methods
a. Configuration Integration Method (CISD)
b. Couple-Cluster Method (CCSD, CCSD(T))
c. Møller–Plesset Perturbation (MP2, MP3, MP4)
d. Quantum Monte-Carlo Method (QMC)
1.6.4. Density Functional Methods
1.6.5. Basis Set
1.6.6. Wavefunction Analysis
1.6.7. Molecular Mechanics
1.6.8. Molecular Dynamics
Force Fields: All-Atom & Coarse-Grain Approaches
1.6.9. Ab initio Molecular Dynamics
1.7.10. Stochastic and Monte Carlo Methods
1.8.11. QM/MM Methods
1.9.12. Simulation and Optimization Techniques
1.7. Book Overview and Organization

2. Conformations, Electronic Structure and Non-covalent Interactions
2.1. Introduction
2.2. Theoretical Approaches
2.2.1. Predicting Molecular Geometry
2.2.2. Z-matrix
2.2.3. Level of Theory
2.2.4. Polarization and Diffuse Functions
2.2.5. External Electric Field and Magnetic Fields
2.2.6. Internal Magnetic Moments
2.2.7. Perturbation Methods
2.2.8. Hybrid Density Functional Methods
2.2.9. BSSE Correction
2.2.10. Bond Dissociation and Angle Bending Energies
2.2.11. Convergence (Total Energy, Geometry, Frequency, Dipole moment)
2.2.12. Potential Energy Surface
2.2.13. Finding Saddle Points
2.2.14. Qualitative Molecular Orbital Theory
2.2.15. Population Analysis Methods
a. Based on the Electrostatic Potential
b. Based on the Electron Density
2.2.16. Natural Bond Orbital Analysis
2.2.17. Weak Interaction Analysis
a. RDG Isosurface Analysis
2.2.18. Quantitative Structure–toxicity Relationship (QSTR) Models for Ionic Liquids
a.Support vector machine (SVM)
b.Heuristic method (HM)
c.Multiple linear regression (MLR)
2.2.19. Linear Free Energy Relationship (LFER) Model
2.3. Chemical Applications
2.3.1. Geometry Optimization and Electron Density Analysis of ILs
2.3.2. Conformational and Topological Analysis of ILs
2.3.3. Studying Molecular Interactions
2.3.4. Predict Effective Charge and Electronic Structure
2.3.5. Molecular Orbitals and Band Gap Calculations
2.3.6. Orbital Composition Analysis
2.3.7. Natural bond orbital (NBO) Analysis of ILs
2.3.8.Analysing Weak Interactions like Coulombic, H-bonding and Hydrogen-halogen interactions
2.3.9. AIM Analysis of Hydrogen-bonds in Ionic Liquids
2.3.10. Simulation of Spectra and Vibrational Assignment
2.3.11. Calculating Aromaticity from Ring Critical Point Analysis
2.3.12. Calculating Ion-pair Interaction Energies
2.3.13. Ploting Density of States of IL ion-pairs
2.3.14. Estimating Aromaticity Index and Double-Bond Equivalent of ILs for Fuel Desulphurization
3.3.15. Predicting and Modelling Eco-toxicity of ILs
2.4 Conclusions

3. Microstructure, Interfacial Properties and Solvation Dynamics in Ionic Liquids
3.1. Introduction
3.2. Theoretical Approaches
3.2.1. Specific Ion Effects and Ionic Liquid Effect
3.2.2. Concentrated Solution Theory
3.2.3. Hole theory
3.2.4. Poisson-Boltzmann theory
3.2.5. Pseudolattice theory models
3.2.6. Self-consistent reaction field models
3.2.7. MD/DFT combined Approaches
3.2.8. Radial Distribution Function (RDF)
3.2.9. Spatial Distribution Function (SDF)
3.2.10. Solvation Models: Long-range and Short-range Interactions
a. Continuum Solvation Models
b. Polarizable Continuum Model (PCM)
c. Conductor-like Screening Models (COSMO-RS, COSMO-SAC)
3.2.11. Improved Four-site Ionic Liquid Coarse-Grain Model
3.2.12. Statistical associating fluid theory (SAFT)
Perturbed-Chain SAFT (PC-SAFT) model
3.2.13. Square-gradient theory
a. Density-gradient theory (DGT)
b. Density-functional theory (DFT)
Local-Density Approximation (LDA)
Weighted-density Approximations (WDA)
Fundamental Measure Theory (FMT)
3.2.14. Hybrid Molecular QSAR (quantitative structure-activity relationship) Model
3.3. Chemical Applications
3.3.1. Simulating Liquid Structure and Effective Charges of ILs
3.3.2. Supramolecular Associations, Template effect and ion-channel formation
3.3.3. Understanding Structural Transitions and Glassy Dynamics
3.3.4. Colloidal stabilization mechanisms by ionic liquids
3.3.5. Quantitative prediction of interfacial properties (interfacial thickness, interfacial tension, adsorption, wetting and confinement effects)
3.3.6.Properties of Ionic Liquids at Charged and Uncharged Interfaces
3.3.7. Interactions of ILs in nano-confined state
3.3.8. Studying sorption of Small Molecules like N2, O2, CO2, CO etc in Ionic Liquids
3.3.9. IL Interaction with carbon-based systems such as CNTs, graphene, C60 etc.
3.3.10. Interaction with macro biomolecules such as Proteins, DNA, RNA etc
3.3.11. CO2 Absorption in Ionic Liquid Reverse Micelle
3.3.12. Studying Properties of IL-based Supramolecular Frame-work Structures
3.3.13. Studying Interactions and Properties of Poly(ionic Liquid) membranes
3.3.14. Bio-solvation using Ionic Liquids
3.3.15. Cellulose Dissolution
3.3.16. ILs for De-nitrification processes
3.4. Conclusions

4. Thermodynamic and Transport Properties in Ionic Liquids
4.1. Introduction
4.2. Theoretical Approaches
4.2.1. Free Energy Methods
4.2.2. Statistical Mechanical Theories of Association in ILs
4.2.3. Fundamental Approaches
a. Born-Oppenheimer (BO) level models
b. McMillan-Mayer (MM) level models
4.2.4. Electrolyte Equation of State (eEoS) Approach
a. Ion-contribution equation of state
b. Perturbed Hard-Sphere (PHS) Equation of State
c. Statistical Associating Fluid Theory (SAFT)
d. Perturbed-chain Statistical Associating Fluid Theory (PC-SAFT)
e. Soft SAFT
g. SAFT-VR and SAFT-VR+DE Models
h. Mean Spherical Approximation (MSA)
i. Shield-sticky Approach
j. Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) equations of state
4.2.5. Group Contribution (GC) Methods
a. QSPR Models
b. GC-type molecular descriptors
c. Gardas−Coutinho GC model
d. Modified UNIFAC (Dortmund) Group Contribution Method
e. GC-artificial neural networks (ANN) methodology
f. GC-Two-layer Feed-forward Artificial Neural Network (FFANN) Model
4.2.6. Linear Yukawa Isotherm Regularity (LYIR)
4.2.7. Differential Evolution (DE) Optimization Method
4.2.8. Scaling Exponent Method
4.2.9. Velocity Autocorrelation Function (VACF) Integration
4.2.10.Modified Quasichemical Model in Pair Approximation
4.2.11. Interstice model
4.2.12. Mean-field DFT and Ion-ion Correlation
4.2.13. Asymmetric Restricted Primitive Model (ARPM)
4.2.14. Activity Coefficient Models: Advantages and Disadvantages
a. Pitzer Models
b. Debye-Huckel (DH) Model
c. Maxwell-Stefan diffusivities
d. Non-random Two Liquid (NRTL) Model
e. UNIQUAC Model
4.3. Chemical Applications
4.3.1. Calculation of Apparent Molar Volume and Density of ILs
4.3.2. Estimating Melting Point and Glass Transition of ILs
4.3.3. Studying Phase Transitions in Ionic Liquids
4.3.4. Calculating Dipole Moment and Dielectric Constant of ILs
4.3.5. Estimating Diffusion Coefficient of ILs
4.3.6. Calculating Radial Distribution Function of ILs
4.3.7. Estimating Electrical Conductivity of ILs
4.3.8. Modelling Thermal Conductivity of ILs
4.3.9. Studying Temperature and Pressure-dependent Viscosity and Surface Tension
4.3.10. Estimating Gas-permeation in ILs
4.3.11.Calculating Osmotic Coefficients and Vapour Pressure of ILs
4.3.12. Modelling Viscosity and Activity Coefficient of ILs
4.3.13. Studying Transport of Ionic Components in IL-based Li ion batteries
4.3.14.Estimating Water Activity of Ionic Liquids
4.3.15.Transport properties of Ionic Liquid Microemulsions
4.3.16. Predicting Vaporization Enthalpy and Entropy Changes
4.3.17. Liquid-vapour Saturation Properties
4.3.18. Modelling Liquid-Liquid and Vapour-Liquid Equilibria of IL, IL/Solvent and IL/Gas Binary Systems
4.3.19. Modelling Ternary Mixtures Containing Ionic Liquids
4.3.20.Thermodynamic Modelling of IL/Metal Salt Mixtures to Estimate Gas Adsorbtivity
4.4 Conclusions

5. Catalytic and Electrochemical Properties in Ionic Liquids
5.1. Introduction
5.2. Theoretical Approaches
5.2.1.Transition State Theory
5.2.2. Poisson-Fermi model
5.2.3. Mean-field Theory
5.2.4. Quantitative Structure–property Relationships (QSPR) method
5.2.5. Explicit Solvent Models
5.2.6. Linear-scaling Pairwise Electrostatic Interaction
5.2.7. OPLS-AA Force Field
5.2.8. QM/MM Methodology
5.3. Chemical Applications
5.3.1. Prediction of Electrochemical Window
5.3.2. Electron Transfer and Redox Phenomenon
5.3.3. Radical, Biradical and Radical-ion Formation
5.3.4.Understanding Capacitance Charging Mechanism of Pure and Mixed IonicLiquids
5.3.5. Studying Ion-Electrode Interactions at Electrode Interface
5.3.6. Estimating Capacitance of a Solvate Ionic Liquid–electrode Interface
5.3.7. Understanding temperature dependence of IL-based electrochemical reactions
5.3.8. Catalytic effect of ILs at electrochemical interfaces of CO2 conversion systems
5.3.9 Studying Kinetics and Dynamics of Ion Transport in Ionic Liquid Electrolytes
5.3.10. Prediciting Chemical and Thermal Stability Window
5.3.11. Predicting Ignition Tendency and Hypergolic Nature
5.3.12. Catalytic Role of ILs in Organic Synthetic Reactions-QSAR
5.3.13. Simulating Chemical Reactions in Ionic Liquids
5.3.14. Understanding Electrical Double Layer Gating based on ILs
5.3.15. Simulating IL-Polymer Interactions in Hybrid Electrolyte-gated Organic Transistors
5.3.16. Studying Kinetics and Mechanism of Protein Unfolding in Ionic Liquids
5.4. Conclusion and Remarks


No. of pages:
© Elsevier 2021
1st November 2020
Paperback ISBN:

About the Editors

Aswathy Joseph

Aswathy Joseph received her Bachelor’s degree and Master’s degrees in Chemistry from the University of Kerala, India, before moving on to Mahatma Gandhi University (MGU), Kottayam, Kerala. She has many publications in reputed international journals including two major reviews. Her areas of research interest are ionic liquids, ferrofluids, IoNanofluids, polymer-ionic liquid thin films and magneto-luminescent nanomaterials. Aswathy has additionally presented many national and international conference papers, and is presently contributing to a number of books based on her research area.

Affiliations and Expertise

Aswathy Bhavan, Elippakuzhy, Thiruvananthapuram, Kerala, India

Suresh Mathew

Suresh Mathew received his M.Sc. in Applied Chemistry from the University of Cochin, India, and his Ph.D. in Chemistry from the University of Kerala, India. He received the Alexander von Humboldt Fellowship for his postdoctoral research at Fraunhofer Institute fur Chemische Technologie (ICT), Karlsruhe, Germany. Currently, he is a Professor of Inorganic Chemistry at the School of Chemical Sciences, Mahatma Gandhi University (MGU), Kerala (India). He is also the Founder Director of the Advanced Molecular Materials Research Centre (AMMRC) at MGU. His areas of research are in nano photocatalysis, ionic liquids, ferrofluids, metal–organic frameworks, eco-friendly propellant oxidizers, and thermal decomposition of solids. He supervises many doctoral and M.Phil students at the department.

Affiliations and Expertise

School of Chemical Sciences (SCS) and Advanced Molecular Materials Research Centre (AMMRC), Mahatma Gandhi University, Kottayam, Kerala, India

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