Molecular Basics of Liquids and Liquid-Based Materials

Preface
Contents
Part I Overview
1 Overview of Liquids and Liquid-Based Systems
Contents
1.1 What Are Liquids?
1.2 Importance of Studies for Solutions and Solvent-Effects
1.3 Properties of Liquids and Solutions: Structure, Dynamics, and Thermodynamics
1.4 Ionic Liquids
1.5 Solvent Effects in Ionic Liquids
1.6 Solvent and Soft Materials
References
Part II Basic Properties of Liquids: Structure and Dynamics
2 Multiscale Solvation Theory for Nano- and Biomolecules
Contents
2.1 Introduction
2.2 Statistical Mechanics Theory of Solvation
2.2.1 3D-RISM Theory
2.2.2 Applications of 3D-RISM Theory for Molecular Recognition in Nano- and Biomolecular Systems
2.3 Electronic Structure Theory in Solution
2.4 Combination with Molecular Simulation
2.5 Summary and Future Perspective
References
3 Dynamics of Molecular Liquids:From Water to Ionic Liquids
Contents
3.1 Interaction-Site Model Description of Molecular Liquids
3.2 Partial Structure Factor and Partial Intermediate Scattering Function
3.2.1 Definition
3.2.2 Scattering Experiment
3.3 Long-Range Limiting Behavior of Partial Intermediate Scattering Functions and Macroscopic Properties
3.3.1 Low-q Limiting Behavior of Self-Part
3.3.2 Low-q Limiting Behavior of Collective Part
3.3.3 Self-Diffusion Coefficient
3.3.4 Rank-1 Reorientational Relaxation
3.3.5 Dielectric Relaxation and Ionic Conductivity
3.4 Generalized Langevin Equation for Intermediate Scattering Function
3.4.1 GLE at Finite Wavevector
3.4.2 Low-q Limiting Behaviors of Memory Function and Current-Current Correlation Function
3.4.3 GLE in Low-q Limit
3.5 Mode-Coupling Theory for Molecular Liquids Based on the Interaction-Site Model
3.5.1 MCT at Finite Wavevector
3.5.2 MCT Expression of Shear Viscosity
3.6 Dynamics of Liquid Water
3.6.1 Dielectric Relaxation
3.6.2 Dynamics of Compressed and Stretched Water
3.7 Effects of Heterogeneous Structure of Room-Temperature Ionic Liquids on Shear Viscosity
3.7.1 Room-Temperature Ionic Liquids
3.7.2 Perera-Mazighi Model and Its Extension
3.7.3 Shear Viscosity
3.7.4 Indirect Role of Heterogeneous Structure
3.8 Summary
References
4 Structure and Dynamics of Liquids Investigated by Quantum Beam: Binary Solution, Solution Under High Pressure, and Confined Solution
Contents
4.1 Quantum Beam Scattering Experiment
4.1.1 Introduction
4.1.2 Structure of Liquids
4.1.3 Dynamics of Liquids
4.2 Scattering Experiment Under High Pressure and Temperature
4.2.1 Introduction
4.2.2 Piston-Cylinder Type Cell
4.2.3 Vessel with Windows
4.2.4 Multi-anvil High-Pressure Cell
4.3 Structure and Dynamics of Alcohol–Water Mixture
4.3.1 Introduction
4.3.2 Structure of Tert-Butanol–Water Mixture
4.3.3 Cluster Dynamic of Butoxyethanol–Water Mixture
4.4 Collective Dynamics of Liquids
4.4.1 Introduction
4.4.2 Van Hove Function
4.4.3 High-Frequency Sound Velocity
4.4.4 Generalize Langevin Equation Analysis
4.4.5 Coupling Between Structural Relaxation and Viscosity
4.4.6 Collective Dynamics of Supercritical Water
4.5 High-Pressure Water
4.5.1 Introduction
4.5.2 Water Structure Under GPa Range
4.5.3 Structure of Electrolyte Solution Under GPa Range
4.6 Confined Water
4.6.1 Introduction
4.6.2 Structure of Confined Water
4.6.3 Dynamics of Confined Water
4.6.4 Confined Solution
4.7 Future Perspectives
References
5 Molecular Theory of Solutionfor Solvation Thermodynamics
Contents
5.1 Introduction
5.2 Combination Between MD Simulation and 3D-RISM Theory
5.2.1 Background
5.2.2 Formalism of MD/3D-RISM Method [24]
5.2.3 Thermodynamic Integration Along the Coupling Parameter Using MD/3D-RISM Simulation [25]
5.2.4 Free Energy Perturbation Along the Coupling Parameter Using MD/3D-RISM Simulation [25]
5.2.5 Thermodynamic Integration Along the Reaction Coordinate Using MD/3D-RISM Simulation [26]
5.2.6 Application of MD/3D-RISM Simulation to 18C6-K+ Complex in Water [25, 26]
5.3 Bridge Correction Toward an Accurate Estimation of the SFE for Molecular Liquids
5.3.1 Background
5.3.2 Improving SFE of Monatomic LJ Solute in Monatomic LJ Solvent: Sigma Enlarging Bridge (SEB) Correction [27, 30, 31]
5.3.3 A Simple Method to Correct the 3D-RISM Theory Using the SEB Function
5.3.4 Hybrid Closure Between the MD Simulation and the OZ Theory [33]
5.3.5 Transferability of the SEB Function for Diatomic LJ Solute Solvated in Monatomic LJ Solvent: 2D-OZ Theory [32, 34, 35]
5.3.6 Transferability of the SEB Function for Diatomic LJ Solute Solvated in Monatomic LJ Solvent: RISM Theory [35]
5.4 Conclusion
Appendix: Variational Principles of the HNC, KH, and KGK Closures
References
6 An Overview on the Dynamics in Aqueous Mixtures of Lower Alcohols
Contents
6.1 Introduction
6.2 Microscopic Dynamics of Fluids
6.2.1 Time Correlation Function Formalism
6.2.2 Hydrogen Bond Dynamics
6.3 Results
6.3.1 Vibrational Dynamics
6.3.2 Rotational Dynamics
6.3.3 Hydrogen Bond Dynamics
6.3.4 Simulation Details
6.4 Conclusion
Conflict of Interest
References
7 Intermolecular Vibrations in Aprotic Molecular Liquids and Ionic Liquids
Contents
7.1 Introduction
7.2 Femtosecond Raman-Induced Kerr Effect Spectroscopy
7.3 Line Shape Analysis of Low-Frequency Kerr Spectra
7.4 General View and Interpretation of Low-Frequency Spectrum in Liquids
7.5 Line Shapes of Low-Frequency Kerr Spectra in Liquids
7.5.1 Aprotic Molecular Liquids
7.5.2 Ionic Liquids
7.6 Relationship Between Low-Frequency Spectrum and Bulk Parameters in Liquids
7.7 Low-Frequency Spectra by THz-TDS and Far-IR
7.8 Toward a Better Understanding of Low-Frequency Spectrum in Liquids: Approach by MD Simulation
7.9 Summary
References
Part III Ionic Liquids
8 Mixing States of Ionic Liquid-Molecular Liquid Mixed Solvents and Their Effects on Metal Complex Formation
Contents
8.1 Introduction
8.2 X-Ray Crystallography
8.3 Stability Constants
8.4 Mixing States of C2mimTFSA and C8mimTFSA with MLs
8.4.1 Acetonitrile
8.4.2 MeOH
8.4.3 DMSO
8.5 Mechanism of Complex Formation
8.6 Conclusions
References
9 Theoretical Approach to Chemical Reactions and Photochemical Processes in Ionic Liquid
Contents
9.1 Introduction
9.2 Chemical Reactions with RISM–SCF–SEDD Methods
9.2.1 RISM, RISM–SCF–SEDD, and Related Methods
9.2.1.1 RISM Theory
9.2.1.2 Structural Fluctuation in RISM
9.2.1.3 RISM–SCF–SEDD Method
9.2.2 Chemical Reactions in the Ground State
9.2.3 Chemical Reactions in the Excited State
9.2.4 Summary
9.3 Solvatochromic Shifts Using QM/MM–MD
9.3.1 Theoretical Methods
9.3.1.1 Conventional QM/MM Simulations for Excitation Energy Calculations
9.3.1.2 Variational Mean-Field Approximation into QM/MM Free Energy
9.3.1.3 Perturbative QM/Polarizable MM Excitation Energy Calculation
9.3.2 Computational Details
9.3.2.1 Procedures of the Mean-Field QM/Polarizable MM and Perturbative Excitation-Energy Calculations
9.3.2.2 Quantum-Chemical Calculations
9.3.2.3 Molecular Mechanics Modeling and Molecular Dynamics Sampling
9.3.3 Results and Discussion
9.3.3.1 Excitation Energy Calculations
9.3.3.2 Solvation Effects of an IL
9.3.4 Summary
9.4 Conclusions
References
10 Local Structure in Mixtures of Ionic Liquid with Molecular Solvent: Vibration Spectroscopy, NMR and Molecular Dynamics Simulation
Contents
10.1 Introduction
10.2 Vibration Spectroscopy
10.3 NMR Chemical Shift
10.3.1 Problems of Chemical Shift Referencing
10.3.2 Chemical Shift Difference
10.3.3 1H-NMR Relative Chemical Shift Variations in IL/Solvents Mixtures
10.4 Molecular Dynamics Simulation
10.4.1 Spatial Distribution Functions
10.4.2 Radial Distribution Functions
10.4.2.1 CationAnion Interaction
10.4.2.2 CationSolvent Interaction
10.4.2.3 Anion–Solvent Interaction
10.4.3 Nearest Neighbor Radial Distribution
References
Part IV Liquid-Based Systems: Biosystems to Soft Materials
11 Amphiphilic, Thermoresponsive Polymers Interacting with Explicit Solvent
Contents
11.1 Introduction: Polymer and Solvent
11.2 Solvation of Polymers at Molecular Level
11.3 How the Intramolecular Interactions Affect the Properties of Polymers in Solution
11.4 Block Design of Amphiphilic Copolymers
11.5 Conclusion
References
12 A Statistical Mechanics Study of the Adsorption Sites of Alkali Ions in Prussian Blue
Contents
12.1 Introduction
12.2 Method of Calculation
12.3 Ions in Bulk Solution
12.4 Adsorption Sites of Alkali Ions in p-PB
12.4.1 Distribution of Water
12.4.2 Distribution of Ions
12.4.3 Explicit Ion and Solvation Structure
12.4.3.1 Solvated Structure of Explicit Li+ and Na+
12.4.3.2 Solvated Structure of Explicit K+ and Cs+
12.5 Adsorption Sites of Alkali Ions in d-PB
12.5.1 Distribution of Water
12.5.2 Distribution of Ions
12.5.3 Explicit Ion and Solvation Structure
12.5.3.1 Solvated Structures of Explicit Li+ and Na+
12.5.3.2 Solvated Structure of Explicit Cs+
12.5.3.3 Solvated Structure of Explicit K+
12.6 Conclusion
References
13 Effects of Antagonistic Salts on Critical Behavior and Order Formation of Soft Matter
Contents
13.1 Introduction
13.2 Effects of Antagonistic Salts on Phase Behavior of Water/Organic Solvent Mixtures
13.3 Charge-Density-Wave Structures Formed in Near-Critical Regions of the Mixtures
13.4 Membrane Structures Formed in the Water-Rich Regions of the Mixtures
13.5 Summary
References
14 Chiral Supramolecular Gels for Visual Enantioselective Recognition Using Sol –Gel Transitions
Contents
14.1 Introduction
14.2 Chiral Recognition by Enantioselective Gel Collapse
14.2.1 Metallogelators
14.2.2 Organic Gelators
14.3 Chiral Recognition by Enantioselective Gelation
14.4 Conclusion
References
15 Organogels and Hydrogels: Functions and Structure Governed by Interactions Between Gelators and Solvents
Contents
15.1 Introduction
15.2 Definitions and Classifications of Gels
15.2.1 Definitions
15.2.2 Structures
15.2.3 Importance of Solvent in the Gel
15.2.4 Classification Depending on Dispersion Medium
15.3 Gel Structures and Properties Depending on the Solvent
15.3.1 Chemical and Physical Gels: Definitions
15.3.2 Organic Gelators: From Small to Big Molecules
15.3.3 Synthesis and Characterization of Gels
15.3.4 Properties Depending on Viscoelasticity and Temperature
15.4 Prediction of Gelation Using Hansen Solubility Parameters
15.4.1 General Aspects
15.4.2 Applications
15.5 Summary and Future Perspective
References
16 Liquid and Gaseous Fuel Mixing in Combustion: A Detailed View from Chemical Reaction Processes
Contents
16.1 Introduction
16.2 Small Length Scales in Reactive Flows
16.3 Wide Time Scale Ranges
16.4 Diffusion Properties of Mixtures Components
16.5 Summary
References
Part V Future Perspective
17 Future Perspectives of Liquids and Liquid-Based Materials
Contents
17.1 Properties of Liquids and Liquid-Based Materials: What and How, Now and Future…
17.2 Liquids and Soft Materials: Specific Characteristics
17.3 Microscopic and Macroscopic Phenomena
17.4 Future Perspectives
17.4.1 Part II: Basic Properties of Liquids: Structure and Dynamics
17.4.2 Part III: Ionic Liquids
17.4.3 Part IV: Liquid-Based Systems: Biosystems to Soft Materials
17.5 Concluding Remarks
References
Index