220
11 Liquid Phase
changes the system energy, but fluctuation contributes little to the system energy on
average.
It is essential to treat water as a crystalline–like structure with well–defined lattice
geometry, strong correlation, and high fluctuation. For a specimen containing N
oxygen atoms, there will be 2N numbers of protons H
+ and lone pairs “:” to form the
O:H–O bonds uniquely, except for the dangling H–O radicals and the dangling lone
pairs at the network terminals. The 2N numbers and the O:H–O bond configuration
conserve regardless of structural phase [49] unless excessive H
+ or “:” is introduced.
The H
+ or the “:” cannot stay alone of moving freely but attach to a H 2 O.
Excessive H
+ injection by acid solvation will bond to a H 2 O to form the H 3 O
+
hydronium and the H↔H anti–HB [50]. Base or H 2 O 2 solvation introduces excessive
number of “:” in the form of HO
− hydroxide that form the O:⇔:O super–HB with
one of its neighboring H 2 O [51]. The H 3 O
+ or the HO
− replaces the central H 2 O in
Fig. 11.1a but the neighboring H 2 O remain their orientations because of the lattice
geometry and interactions with other neighboring H 2 O molecules. The H 3 O
+ or the
HO
− may undergo Brownian motion or drift diffusion under a graded electric or
thermal field.
The motion of a H 2 O molecule or the proton H
+ transportation is subject to
restriction. If the central molecule rotate above 60° around the C 3v symmetrical axis
of the 2H 2 O unit cell, an H↔H and O:⇔:O repulsion will come into play, which is
energetically forbidden. Because of the H–O bond energy of ~4.0 eV, translational
tunneling of the H
+ between adjacent H 2 O molecules is also forbidden. In fact, only
can 121.6 nm wavelength laser radiation breaks the H–O or the D–O bond in the
vapor phase [52, 53]. The 121.6 nm wavelength corresponds to 5.1 eV energy that is
greater than the 4.0 eV estimated by resolving the T C − P profiles of ice Regelation
[54, 55]. The least molecular coordination number of the gaseous monomer shortens
and stiffens the H–O bond most.
11.2.2 O:H–O Bond Potentials and Cooperativity
Figure 11.1b illustrates the asymmetrical, short–range, coupled three–body potentials
for the segmented O:H–O bond [44, 45]. The proton serves as the coordination origin.
The left–hand side is the O:H van der Walls (vdW) interaction and the right–hand
side is the H–O polar-covalent bond. The Coulomb repulsion between electron pairs
on neighboring O
2− couple the O:H–O bond to be an oscillator pair.
The O:H nonbond and the H–O bond segmental disparity and the O–O coupling
dislocate the O
2− of the segmented O:H–O bond in the same direction but by different
amounts under an external stimulus, see Fig. 11.1c. The softer O:H nonbond always
relaxes more than the stiffer H–O bond with respect to the H
+ as the coordination
origin. The ∠O:H–O angle θ relaxation contributes mainly to the geometry and
mass density. The O:H–O bond bending has its specific vibration mode that does
not interfere with the H–O and the O:H stretching vibrations [1]. The O:H–O bond
cooperativity determines the properties of water and ice under external stimulus such
11 Liquid Phase
changes the system energy, but fluctuation contributes little to the system energy on
average.
It is essential to treat water as a crystalline–like structure with well–defined lattice
geometry, strong correlation, and high fluctuation. For a specimen containing N
oxygen atoms, there will be 2N numbers of protons H
+ and lone pairs “:” to form the
O:H–O bonds uniquely, except for the dangling H–O radicals and the dangling lone
pairs at the network terminals. The 2N numbers and the O:H–O bond configuration
conserve regardless of structural phase [49] unless excessive H
+ or “:” is introduced.
The H
+ or the “:” cannot stay alone of moving freely but attach to a H 2 O.
Excessive H
+ injection by acid solvation will bond to a H 2 O to form the H 3 O
+
hydronium and the H↔H anti–HB [50]. Base or H 2 O 2 solvation introduces excessive
number of “:” in the form of HO
− hydroxide that form the O:⇔:O super–HB with
one of its neighboring H 2 O [51]. The H 3 O
+ or the HO
− replaces the central H 2 O in
Fig. 11.1a but the neighboring H 2 O remain their orientations because of the lattice
geometry and interactions with other neighboring H 2 O molecules. The H 3 O
+ or the
HO
− may undergo Brownian motion or drift diffusion under a graded electric or
thermal field.
The motion of a H 2 O molecule or the proton H
+ transportation is subject to
restriction. If the central molecule rotate above 60° around the C 3v symmetrical axis
of the 2H 2 O unit cell, an H↔H and O:⇔:O repulsion will come into play, which is
energetically forbidden. Because of the H–O bond energy of ~4.0 eV, translational
tunneling of the H
+ between adjacent H 2 O molecules is also forbidden. In fact, only
can 121.6 nm wavelength laser radiation breaks the H–O or the D–O bond in the
vapor phase [52, 53]. The 121.6 nm wavelength corresponds to 5.1 eV energy that is
greater than the 4.0 eV estimated by resolving the T C − P profiles of ice Regelation
[54, 55]. The least molecular coordination number of the gaseous monomer shortens
and stiffens the H–O bond most.
11.2.2 O:H–O Bond Potentials and Cooperativity
Figure 11.1b illustrates the asymmetrical, short–range, coupled three–body potentials
for the segmented O:H–O bond [44, 45]. The proton serves as the coordination origin.
The left–hand side is the O:H van der Walls (vdW) interaction and the right–hand
side is the H–O polar-covalent bond. The Coulomb repulsion between electron pairs
on neighboring O
2− couple the O:H–O bond to be an oscillator pair.
The O:H nonbond and the H–O bond segmental disparity and the O–O coupling
dislocate the O
2− of the segmented O:H–O bond in the same direction but by different
amounts under an external stimulus, see Fig. 11.1c. The softer O:H nonbond always
relaxes more than the stiffer H–O bond with respect to the H
+ as the coordination
origin. The ∠O:H–O angle θ relaxation contributes mainly to the geometry and
mass density. The O:H–O bond bending has its specific vibration mode that does
not interfere with the H–O and the O:H stretching vibrations [1]. The O:H–O bond
cooperativity determines the properties of water and ice under external stimulus such