24.2 O:H–O Bond Segmental Cooperativity
477
1 number of protons and 2N-1 lone pairs in the solution. The excessive 2N + 1–
(2N−1) = 2 protons form uniquely an H
+
↔H
+ anti–HB without any other choice.
The H 3 O
+ remains the tetrahedron configuration having three H–O bonds and one
lone pair, which is similar to the situation of H 2n+1 O
+
2n cluster formation with n = 2
and 4 [27] but no freely shuttling between oxygen ions or hopping from one site to
another.
Likewise, the YOH base is dissolved into a Y
+ cation and a hydroxide (HO
− is
HF-like tetrahedron with three lone pairs and one H
+ ). The HO
− addition transits
the 2 N conservation into 2N + 3 number of lone pairs “:” and 2N + 1 number of
protons. The excessively unbalanced 2N + 3–(2N + 1) = 2 lone pairs can only form
the O:⇔:O point compressor between the central HO
− and one of its H 2 O neighbors
that reserve their molecular orientations. This O:⇔:O compressor pertaining to each
hydroxide has the same effect of but stronger mechanical compression on the network
HB relaxation [22] because of the clustering of the two pairs of lone pairs and their
weak binding energy to O
2− . The clustering of four electrons and weak bonding to
O
2− specify the point polarizer instead of a point breaker. X
− and Y
+ in all solutions
only polarize their neighboring H 2 O molecules to form hydration shells.
24.3 DPS of Water and Solutions
The DPS distils only phonons transiting into their hydration states as a peak above
the x–axis, which equals the abundance loss of the ordinary HBs as a valley below
the axis in the DPS spectrum. This process removes the spectral areas commonly–
shared by the ordinary water and the high–order hydration shells. The DPS resolves
the transition of the phonon stiffness (frequency shift) and abundance (peak area) by
solvation. The fraction coefficient, f x (C), being the integral of the DPS peak, is the
fraction of bonds, or the number of phonons transiting from water to the hydration
states at a solute concentration C.
YOH solvation broadens the main peak shifting to lower frequencies [28–30].
The solute type and concentration resolved DPS shown in Fig. 24.4 confirmed that
YOH solvation indeed softens the ω H phonon—O:⇔:O compression lengthens the
neighboring H–O bond and softens its phonon to 3100 cm
−1 and below. Besides, a
sharp peak appears at 3610 cm
−1 that is identical to the dangling H–O bond at water
surface. The sharp peaks feature the less ordered H–O bond due the HO − . The ω x
is less sensitive to the type of the alkali cations of the same concentration. These
observations confirm that the O:⇔:O super–HB has the same but stronger effect of
mechanical compression [31] and that the BOLS correlation [32] applies to aqueous
solutions—intramolecular bonds of undercoordinated molecules become shorter and
stronger.
Observations justify that the O:⇔:O super–HB point compression (<3100 cm
−1 ;
>220 cm
−1 ) has the same but much stronger effect of mechanically bulk compression
(<3300 cm
−1 ; >200 cm
−1 ) at the critical pressure 1.33 GPa for the room-temperature
water-ice transition [22], compared to the compression effect on water and ice. The
477
1 number of protons and 2N-1 lone pairs in the solution. The excessive 2N + 1–
(2N−1) = 2 protons form uniquely an H
+
↔H
+ anti–HB without any other choice.
The H 3 O
+ remains the tetrahedron configuration having three H–O bonds and one
lone pair, which is similar to the situation of H 2n+1 O
+
2n cluster formation with n = 2
and 4 [27] but no freely shuttling between oxygen ions or hopping from one site to
another.
Likewise, the YOH base is dissolved into a Y
+ cation and a hydroxide (HO
− is
HF-like tetrahedron with three lone pairs and one H
+ ). The HO
− addition transits
the 2 N conservation into 2N + 3 number of lone pairs “:” and 2N + 1 number of
protons. The excessively unbalanced 2N + 3–(2N + 1) = 2 lone pairs can only form
the O:⇔:O point compressor between the central HO
− and one of its H 2 O neighbors
that reserve their molecular orientations. This O:⇔:O compressor pertaining to each
hydroxide has the same effect of but stronger mechanical compression on the network
HB relaxation [22] because of the clustering of the two pairs of lone pairs and their
weak binding energy to O
2− . The clustering of four electrons and weak bonding to
O
2− specify the point polarizer instead of a point breaker. X
− and Y
+ in all solutions
only polarize their neighboring H 2 O molecules to form hydration shells.
24.3 DPS of Water and Solutions
The DPS distils only phonons transiting into their hydration states as a peak above
the x–axis, which equals the abundance loss of the ordinary HBs as a valley below
the axis in the DPS spectrum. This process removes the spectral areas commonly–
shared by the ordinary water and the high–order hydration shells. The DPS resolves
the transition of the phonon stiffness (frequency shift) and abundance (peak area) by
solvation. The fraction coefficient, f x (C), being the integral of the DPS peak, is the
fraction of bonds, or the number of phonons transiting from water to the hydration
states at a solute concentration C.
YOH solvation broadens the main peak shifting to lower frequencies [28–30].
The solute type and concentration resolved DPS shown in Fig. 24.4 confirmed that
YOH solvation indeed softens the ω H phonon—O:⇔:O compression lengthens the
neighboring H–O bond and softens its phonon to 3100 cm
−1 and below. Besides, a
sharp peak appears at 3610 cm
−1 that is identical to the dangling H–O bond at water
surface. The sharp peaks feature the less ordered H–O bond due the HO − . The ω x
is less sensitive to the type of the alkali cations of the same concentration. These
observations confirm that the O:⇔:O super–HB has the same but stronger effect of
mechanical compression [31] and that the BOLS correlation [32] applies to aqueous
solutions—intramolecular bonds of undercoordinated molecules become shorter and
stronger.
Observations justify that the O:⇔:O super–HB point compression (<3100 cm
−1 ;
>220 cm
−1 ) has the same but much stronger effect of mechanically bulk compression
(<3300 cm
−1 ; >200 cm
−1 ) at the critical pressure 1.33 GPa for the room-temperature
water-ice transition [22], compared to the compression effect on water and ice. The