24.1 Water and Aqueous Solutions
473
and orientation conserve in the solvent, the polarization allows the oriented H 2 O
molecules only rotate slightly. The cation locates eccentrically by some 0.8 Å in the
interstitial hollow site to polarize and relax its surroundings anisotropically [11].
This situation also applies to solvation of other solutes. The intrinsic electric field
will trap the intestinal neutral molecules such as H 2 or charged ions, such as X
−
and Y
+ at solvation of acid, base, and salt. Only lone pairs and protons existing in
the form of OH
− and H 3 O
+ can replace the H 2 O to form the (OH
− ; H 3 O
+ ):4H 2 O
associated with H↔H anti-HB and O:⇔:O super-HB [12].
The vibration mode features the Fourier transformation of bonds vibrating in the
similar frequencies regardless of their orientations and locations in real space. The
peak shape is the population function and the peak maximum the highest popularity.
The peak central ω x represents the stiffness of the vibrating bonds as a function of
bond length d x and bond energy E x , (ω x )
2
∝ E x /d
2
x . The peak integral is proportional
to the number of bonds contributing to the phonon abundance of the vibration mode
x. Thus, one can distill the fraction-stiffness transition of the O:H–O phonons by
differentiating the spectrum collected from deionized water as a reference from those
collected from solutions or water under perturbation such as heating and compressing
upon all the spectral peak being area normalized [13]. This DPS strategy gives direct
information on the O:H–O bonds transition from its vibration mode of ordinary
water to the hydrating in terms of the number fraction (phonon abundance), stiffness
(frequency shift), and fluctuation (line width) with much more ease and quantitative
information than using the conventional spectral peak Gaussian-type decomposition.
24.2 O:H–O Bond Segmental Cooperativity
There are regulations for the O:H–O bond and the structure order of liquid water
[1]. Water prefers a crystalline–like structure with well–defined lattice geometry,
strong correlation, and high fluctuation. The 2H 2 O unit cell (or 2H 2 O motif) of
C 3v symmetry having four HBs bridging oxygen anions. For a specimen containing N number of O
2− anions, there are 2 N protons H
+ and 2 N lone pairs “:” and
the O:H–O bond configuration conserve regardless of structural phase [14] unless
excessive H
+ or “:” is introduced [7, 8]. The O:⇔:O inter-lone-pair repulsion couples the O:H van der Walls bond and the H–O intramolecular interactions to form
the O:H–O bond that serves as the coupled oscillator pair. This oscillator features the
energetics and dynamics of water ice, in terms of hydrogen bond segmental cooperative relax-ability. The segmental vibration frequency and bonding energy define the
specific-heat capacity. The superposition of the segmental specific heats determine
the thermodynamics of water ice and the phase structures at the ambient pressure,
see Fig. 24.3. The specific-heat defines the structure phases at the ambient pressure,
density anomalies, and the quasisolid (QS) phase of cooling expansion.
The motion of a H 2 O molecule or the tunneling transport of a proton H
+ is subject
to restriction. If the central H 2 O rotates 60° or above around the C 3v symmetrical axis
of the 2H 2 O, there will be a H↔H anti–HB and an O:⇔:O super–HB formed, which
473
and orientation conserve in the solvent, the polarization allows the oriented H 2 O
molecules only rotate slightly. The cation locates eccentrically by some 0.8 Å in the
interstitial hollow site to polarize and relax its surroundings anisotropically [11].
This situation also applies to solvation of other solutes. The intrinsic electric field
will trap the intestinal neutral molecules such as H 2 or charged ions, such as X
−
and Y
+ at solvation of acid, base, and salt. Only lone pairs and protons existing in
the form of OH
− and H 3 O
+ can replace the H 2 O to form the (OH
− ; H 3 O
+ ):4H 2 O
associated with H↔H anti-HB and O:⇔:O super-HB [12].
The vibration mode features the Fourier transformation of bonds vibrating in the
similar frequencies regardless of their orientations and locations in real space. The
peak shape is the population function and the peak maximum the highest popularity.
The peak central ω x represents the stiffness of the vibrating bonds as a function of
bond length d x and bond energy E x , (ω x )
2
∝ E x /d
2
x . The peak integral is proportional
to the number of bonds contributing to the phonon abundance of the vibration mode
x. Thus, one can distill the fraction-stiffness transition of the O:H–O phonons by
differentiating the spectrum collected from deionized water as a reference from those
collected from solutions or water under perturbation such as heating and compressing
upon all the spectral peak being area normalized [13]. This DPS strategy gives direct
information on the O:H–O bonds transition from its vibration mode of ordinary
water to the hydrating in terms of the number fraction (phonon abundance), stiffness
(frequency shift), and fluctuation (line width) with much more ease and quantitative
information than using the conventional spectral peak Gaussian-type decomposition.
24.2 O:H–O Bond Segmental Cooperativity
There are regulations for the O:H–O bond and the structure order of liquid water
[1]. Water prefers a crystalline–like structure with well–defined lattice geometry,
strong correlation, and high fluctuation. The 2H 2 O unit cell (or 2H 2 O motif) of
C 3v symmetry having four HBs bridging oxygen anions. For a specimen containing N number of O
2− anions, there are 2 N protons H
+ and 2 N lone pairs “:” and
the O:H–O bond configuration conserve regardless of structural phase [14] unless
excessive H
+ or “:” is introduced [7, 8]. The O:⇔:O inter-lone-pair repulsion couples the O:H van der Walls bond and the H–O intramolecular interactions to form
the O:H–O bond that serves as the coupled oscillator pair. This oscillator features the
energetics and dynamics of water ice, in terms of hydrogen bond segmental cooperative relax-ability. The segmental vibration frequency and bonding energy define the
specific-heat capacity. The superposition of the segmental specific heats determine
the thermodynamics of water ice and the phase structures at the ambient pressure,
see Fig. 24.3. The specific-heat defines the structure phases at the ambient pressure,
density anomalies, and the quasisolid (QS) phase of cooling expansion.
The motion of a H 2 O molecule or the tunneling transport of a proton H
+ is subject
to restriction. If the central H 2 O rotates 60° or above around the C 3v symmetrical axis
of the 2H 2 O, there will be a H↔H anti–HB and an O:⇔:O super–HB formed, which