Contents
1 A Historical Review of the Structures of Water and Ice . . . . . . . . . .
1
1.1 What is “Structure” for Liquid Water? . . . . . . . . . . . . . . . . . . . . .
1
1.2 Bragg Scattering and Bernal–Fowler Water . . . . . . . . . . . . . . . . .
3
1.2.1 Scattering of X-Rays by Liquid Water . . . . . . . . . . . . . . .
4
1.2.2 X-Ray Crystallography of Ice . . . . . . . . . . . . . . . . . . . . . .
7
1.2.3 The Radial Distribution Function . . . . . . . . . . . . . . . . . . . 11
1.3 Direct Current Conductivity and pH of Water . . . . . . . . . . . . . . . 17
1.3.1 Electrical Conduction Mechanism . . . . . . . . . . . . . . . . . . . 17
1.3.2 The Autoionization of Water . . . . . . . . . . . . . . . . . . . . . . 20
1.3.3 Pondus Hydrogenii (pH) . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.4 Self-diffusion by Isotopic Tracers . . . . . . . . . . . . . . . . . . . . . . . . 26
1.5 Diffusion by Neutron Scattering . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.6 Water in Molecular-Dynamic Simulations . . . . . . . . . . . . . . . . . . 35
1.6.1 Methods of Water Modeling . . . . . . . . . . . . . . . . . . . . . . . 35
1.6.2 The Simulation of the Electrodynamic Parameters
of Water and Ice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
1.7 Summary of the “Structure” of Water and Ice . . . . . . . . . . . . . . . 41
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2 The Interaction of Electromagnetic Waves with Water . . . . . . . . . . 51
2.1 Maxwell’s Equations in the Presence of Water . . . . . . . . . . . . . . . 51
2.2 The Broadband Dielectric Spectroscopy of Water . . . . . . . . . . . . . 55
2.3 Microwave Spectrum: Dielectric Relaxation . . . . . . . . . . . . . . . . . 57
2.3.1 Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.3.2 Data Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.3 Is Debye Relaxation a Unique Feature of Water? . . . . . . . 67
2.4 The Static Dielectric Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.4.1 Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.4.2 The Local-Field Approach . . . . . . . . . . . . . . . . . . . . . . . . 71
2.4.3 Intermolecular Polarization Approach . . . . . . . . . . . . . . . . 74
xi
1 A Historical Review of the Structures of Water and Ice . . . . . . . . . .
1
1.1 What is “Structure” for Liquid Water? . . . . . . . . . . . . . . . . . . . . .
1
1.2 Bragg Scattering and Bernal–Fowler Water . . . . . . . . . . . . . . . . .
3
1.2.1 Scattering of X-Rays by Liquid Water . . . . . . . . . . . . . . .
4
1.2.2 X-Ray Crystallography of Ice . . . . . . . . . . . . . . . . . . . . . .
7
1.2.3 The Radial Distribution Function . . . . . . . . . . . . . . . . . . . 11
1.3 Direct Current Conductivity and pH of Water . . . . . . . . . . . . . . . 17
1.3.1 Electrical Conduction Mechanism . . . . . . . . . . . . . . . . . . . 17
1.3.2 The Autoionization of Water . . . . . . . . . . . . . . . . . . . . . . 20
1.3.3 Pondus Hydrogenii (pH) . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.4 Self-diffusion by Isotopic Tracers . . . . . . . . . . . . . . . . . . . . . . . . 26
1.5 Diffusion by Neutron Scattering . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.6 Water in Molecular-Dynamic Simulations . . . . . . . . . . . . . . . . . . 35
1.6.1 Methods of Water Modeling . . . . . . . . . . . . . . . . . . . . . . . 35
1.6.2 The Simulation of the Electrodynamic Parameters
of Water and Ice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
1.7 Summary of the “Structure” of Water and Ice . . . . . . . . . . . . . . . 41
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2 The Interaction of Electromagnetic Waves with Water . . . . . . . . . . 51
2.1 Maxwell’s Equations in the Presence of Water . . . . . . . . . . . . . . . 51
2.2 The Broadband Dielectric Spectroscopy of Water . . . . . . . . . . . . . 55
2.3 Microwave Spectrum: Dielectric Relaxation . . . . . . . . . . . . . . . . . 57
2.3.1 Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.3.2 Data Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.3 Is Debye Relaxation a Unique Feature of Water? . . . . . . . 67
2.4 The Static Dielectric Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.4.1 Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.4.2 The Local-Field Approach . . . . . . . . . . . . . . . . . . . . . . . . 71
2.4.3 Intermolecular Polarization Approach . . . . . . . . . . . . . . . . 74
xi