20.1 Scope
371
temperature, atomic cohesive energy, thermal expansion coefficient, compressibility,
elastic modulus, binding energy density, which should be the right capability of the
spectrometrics. It is uncovered that the single dimer-vibration and the collective
dimer-vibration govern, respectively, the number-of-layer reduction induced blue
and red phonon frequency shift. The slope of the Debye thermal decay of the ω(T),
∂ω/∂T, at higher temperatures is the inverse of atomic cohesive energy and the
pressure slope of the ω(P) profile, or the ∂ω/∂P, approaches the inverse of binding
energy density.
Chapter 23 proved first the core-shell structures of water droplets and nanocrystals
with derive of the skin thickness of 0.09 nm for the water droplets and two atomic
diameters, 0.5 nm for CeO 2 nanocrystals. The skins follow the universal bond orderlength-strength (BOLS) notion that specify the shorter and stiffer bonds between
undercoordinated atoms. Examination of the sized crystals from nanoscale to the bulk
of group IV, III-nitride, II-oxide under the perturbations of size reduction, pressure
and temperature derived the same kind information described in Sect. 20.3.
Chapter 24 briefly introduces the recent progress in the spectrometrics of water
ice and aqueous solutions. The effect of pressure, temperature, molecular undercoordination, and charge injection by acid, base, and salt solvation on the performance of
water ice was systematically examined. Aqueous charge injection by solvation in the
forms of anions, cations, electrons, lone pairs, molecular dipoles, and protons modulates the hydrogen bonding (O:H–O or HB) and electronic dynamics and properties
of a solution. The modulation is through O:H formation, O:H–O bond relaxation,
H ↔ H anti-HB and O:⇔:O super-HB repulsions, electrostatically screened polarization, solute-solute interaction, and the solute H–O bond contraction due to bond
order deficiency. Polarization by charge injection and molecular undercoordination
modify the critical pressures and temperatures for the confined ice-quasisolid and
the salted water-ice phase transition under heating and compression. Consistency
between theoretical predictions and measurements confirms the ever-unaware issues
such as quasisolid phase of negative thermal expansion (NTE) due to O:H–O bond
segmental specific heat disparity. Molecular coordination deficiency and electrostatic
polarization result in the supersolid phase. Excessive protons and lone pairs form the
H 3 O
+ hydronium and HO
− hydroxide, which turns an O:H–O bond into the H ↔ H
anti–HB upon acid solvation and O:⇔:O super–HB on base solvation. The aqueous
molecular nonbonding can extend to other molecular crystals and to the negative
thermal expansion of other solid substance.
Chapter 25 summarizes the attainment, limitation, and forward-looking directions.
The phonon spectrometrics detects directly the bond responding to perturbation but
the electron spectrometrics probes the behavior of electrons in various bands/levels
due to bond relaxation, which are totally different but complement each other. This
set of spectrometrics provides a powerful technique applicable to situations when
electrons and phonons are involved and under any external perturbation—for atomistic, dynamic, local, and quantitative information on bond and electron performance
and consistent insight into the nature of observations, an essential theoretical and
experimental strategies for functional materials devising.
371
temperature, atomic cohesive energy, thermal expansion coefficient, compressibility,
elastic modulus, binding energy density, which should be the right capability of the
spectrometrics. It is uncovered that the single dimer-vibration and the collective
dimer-vibration govern, respectively, the number-of-layer reduction induced blue
and red phonon frequency shift. The slope of the Debye thermal decay of the ω(T),
∂ω/∂T, at higher temperatures is the inverse of atomic cohesive energy and the
pressure slope of the ω(P) profile, or the ∂ω/∂P, approaches the inverse of binding
energy density.
Chapter 23 proved first the core-shell structures of water droplets and nanocrystals
with derive of the skin thickness of 0.09 nm for the water droplets and two atomic
diameters, 0.5 nm for CeO 2 nanocrystals. The skins follow the universal bond orderlength-strength (BOLS) notion that specify the shorter and stiffer bonds between
undercoordinated atoms. Examination of the sized crystals from nanoscale to the bulk
of group IV, III-nitride, II-oxide under the perturbations of size reduction, pressure
and temperature derived the same kind information described in Sect. 20.3.
Chapter 24 briefly introduces the recent progress in the spectrometrics of water
ice and aqueous solutions. The effect of pressure, temperature, molecular undercoordination, and charge injection by acid, base, and salt solvation on the performance of
water ice was systematically examined. Aqueous charge injection by solvation in the
forms of anions, cations, electrons, lone pairs, molecular dipoles, and protons modulates the hydrogen bonding (O:H–O or HB) and electronic dynamics and properties
of a solution. The modulation is through O:H formation, O:H–O bond relaxation,
H ↔ H anti-HB and O:⇔:O super-HB repulsions, electrostatically screened polarization, solute-solute interaction, and the solute H–O bond contraction due to bond
order deficiency. Polarization by charge injection and molecular undercoordination
modify the critical pressures and temperatures for the confined ice-quasisolid and
the salted water-ice phase transition under heating and compression. Consistency
between theoretical predictions and measurements confirms the ever-unaware issues
such as quasisolid phase of negative thermal expansion (NTE) due to O:H–O bond
segmental specific heat disparity. Molecular coordination deficiency and electrostatic
polarization result in the supersolid phase. Excessive protons and lone pairs form the
H 3 O
+ hydronium and HO
− hydroxide, which turns an O:H–O bond into the H ↔ H
anti–HB upon acid solvation and O:⇔:O super–HB on base solvation. The aqueous
molecular nonbonding can extend to other molecular crystals and to the negative
thermal expansion of other solid substance.
Chapter 25 summarizes the attainment, limitation, and forward-looking directions.
The phonon spectrometrics detects directly the bond responding to perturbation but
the electron spectrometrics probes the behavior of electrons in various bands/levels
due to bond relaxation, which are totally different but complement each other. This
set of spectrometrics provides a powerful technique applicable to situations when
electrons and phonons are involved and under any external perturbation—for atomistic, dynamic, local, and quantitative information on bond and electron performance
and consistent insight into the nature of observations, an essential theoretical and
experimental strategies for functional materials devising.