Chapter 1
A Historical Review of the Structures
of Water and Ice
Abstract The details of the structure of water are important for understanding its
dielectric properties and vice versa, because the nuclei and electrons of water particles
are, in essence, charges interacting with each other and with external fields. Although
water has been studied like no other substance, its atomic-molecular dynamics (both
individual and collective) are still under discussion. Bernal–Fowler 100-year-old
paradigm, based on early diffraction data, requires critical analysis. In this chapter, I
consider the history of the notion of “water structure,” which includes several milestones related to the appearance of particular experimental and theoretical methods.
I discuss early electrical conductivity measurements, X-ray diffraction and neutron
scattering techniques, pH measurements, isotopic tracer diffusion, nuclear magnetic
resonance, and simulations of molecular dynamics. All these techniques and methods have significantly contributed to the development of the concept of hydrogen
bonding in water and related substances. However, recent studies have shown that
classic models still fail to reproduce the basic electrodynamic parameters of water
and ice, and need to be improved.
1.1 What is “Structure” for Liquid Water?
The concept of “structure” for a liquid differs from that which is usually applied to
solid crystalline materials. At first glance, a liquid is a fluid that has no shape without
a container or confining medium, so it seems to have no “structure” at all, like a gas.
Liquids are also essentially incompressible, maintaining the intermolecular distance
and having a volume that is nearly as constant as in solids. One could say that this
is due to the translational movement of its molecular species, a movement that is
forbidden for ice molecules. However, glaciers, which are made of ice, slide and
move, and this implies a translational degree of freedom, but this process appears
on the much larger timescale. So, what does “structure” means for water and ice?
Although water, strictly speaking, refers to the gaseous, liquid, or solid forms, water
is used in the text to refer to liquid water, unless otherwise stated.
Although long-range order is not observed in water and is only a feature of carefully prepared ice samples, the concept of short-range order, in contrast, is fully
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2021
V. Artemov, The Electrodynamics of Water and Ice, Springer Series
in Chemical Physics 124, https://doi.org/10.1007/978-3-030-72424-5_1
1
A Historical Review of the Structures
of Water and Ice
Abstract The details of the structure of water are important for understanding its
dielectric properties and vice versa, because the nuclei and electrons of water particles
are, in essence, charges interacting with each other and with external fields. Although
water has been studied like no other substance, its atomic-molecular dynamics (both
individual and collective) are still under discussion. Bernal–Fowler 100-year-old
paradigm, based on early diffraction data, requires critical analysis. In this chapter, I
consider the history of the notion of “water structure,” which includes several milestones related to the appearance of particular experimental and theoretical methods.
I discuss early electrical conductivity measurements, X-ray diffraction and neutron
scattering techniques, pH measurements, isotopic tracer diffusion, nuclear magnetic
resonance, and simulations of molecular dynamics. All these techniques and methods have significantly contributed to the development of the concept of hydrogen
bonding in water and related substances. However, recent studies have shown that
classic models still fail to reproduce the basic electrodynamic parameters of water
and ice, and need to be improved.
1.1 What is “Structure” for Liquid Water?
The concept of “structure” for a liquid differs from that which is usually applied to
solid crystalline materials. At first glance, a liquid is a fluid that has no shape without
a container or confining medium, so it seems to have no “structure” at all, like a gas.
Liquids are also essentially incompressible, maintaining the intermolecular distance
and having a volume that is nearly as constant as in solids. One could say that this
is due to the translational movement of its molecular species, a movement that is
forbidden for ice molecules. However, glaciers, which are made of ice, slide and
move, and this implies a translational degree of freedom, but this process appears
on the much larger timescale. So, what does “structure” means for water and ice?
Although water, strictly speaking, refers to the gaseous, liquid, or solid forms, water
is used in the text to refer to liquid water, unless otherwise stated.
Although long-range order is not observed in water and is only a feature of carefully prepared ice samples, the concept of short-range order, in contrast, is fully
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2021
V. Artemov, The Electrodynamics of Water and Ice, Springer Series
in Chemical Physics 124, https://doi.org/10.1007/978-3-030-72424-5_1
1