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NaCl solvation turns the fS portion molecules into the hydrating supersolid phase by ionic polarization and leaves the rest fO portion ordinary. Polarization shortens and stiffens the HO bond and does the O:H nonbond contrastingly in the supersolid. Water absorbs energy by HO cooling contraction in the quasisolid phase during the transition from Liquid to Quasisolid and then Ice The solution R drops with the fO loss till zero corresponding to 10 water molecules that saturates the solvation per solute at least. The polarization-weakening of the O H nonbonds lowers the TN to 253 K or below of the supersolid phase.

The segmental specific heat ratio of the couple hydrogen bond defines not only the phase of Vapor, Liquid, Ice I and XI phase with a quasisolid phase that shows the negative thermal extensibility but uniquely the slope of density of water ice in different phases. Ice floats because H-O contracts less than O:H expands in the QS phase at cooling., 6 pages, 4 figures

Atomic undercoordination fascinates defects, surfaces, and nanostructures in electronic binding energy, lattice oscillation frequency, elasticity and plasticity (IHPR), thermal stability, photon emisibility, reactivity, dielectrics, super-hydrophobicity, spin-resolved topological edge and monolayer high-TC superconductivity, etc., through local bond contraction, quantum entrapment and polarization., Comment: 33 pages 15 figure, Nanomaterials science 2020

Atomic undercoordination, charge injection, mechanical and thermal activation mediate the properties of a material intrinsically by bond relaxation from one equilibrium to another while the phonon spectrometrics probes the ever-unexpected information of the binding energy density, atomic cohesive energy, single bond force constant, crystal elastic modulus, Debye temperature and the abundance-length-stiffness transition of bonds under perturbation., Comment: 39 k Words, 41 figs, 371 refs

Although the phase of water has extensively investigated whether there exists a defect distorting only locally the structure still under debate. Here we report a localized 5775 defect phase presented in the double layer ice on the Au (111) surface, which is a metastable structure with 5- and 7-membered rings compared with a perfect hexagonal one. Without altering the total number of the hydrogen bonds of the ice, the defect only introduces 0.08 {\AA} molecular displacement and 3.27% interaction energy change outside the defected area. Such defect also exists without Au support but causes a larger lattice relaxation or smaller interaction energy change. The excessively high barrier as well as the low quantum tunneling and thermodynamic probabilities hinder the formation of the defect by post-grown isomerization from the perfect to the defected structure. This finding indicates that the defected ice is stable, and the defect can be formed during the ice growth stage., Comment: 12 pages, 2 figures

A combination of the temporally and spatially resolved phonon spectroscopy has enabled calibration of hydrogen bond transition from the vibration mode of heavy water to the core/shelled nanodroplet and the subnanosized ionic hydration shell in terms of phonon abundance/lifetime/stiffness. It is uncovered that charge injection by salt solvation and skin formation by molecular undercoordination (often called confinement) share the same supersolidity of HO (DO as a probe) bond contraction, O:H elongation, and electron polarization. The bond transition stems the solution viscosity, surface stress, and slows down the molecular dynamics. The skin reflection further hinders phonon energy dissipation and thus lengthens the phonon lifetime of the nanodroplet.

Charge injection in terms of anions, cations, electrons, lone pairs, protons, and molecular dipoles by acid,base, salt and organic molecular solvation mediates the O:HO bonding network and properties of the solution through O:H formation, HH fragillization, O:=:O compression, electrostatic polarization, H2O dipolar shielding, and solute/solute interaction, Comment: 45 pages. arXiv admin note: substantial text overlap with arXiv:1811.11827

We investigated the bond, electronic and magnetic behavior of adsorption Yttrium atoms on Lithium (110) surface using a combination of Bond-order-length-strength(BOLS) correlation and density-functional theory(DFT). We found that adsorption Y atoms on Li(110) surfaces form two-dimensional (2D) geometric structures of hexagon, nonagon, solid hexagonal, quadrangle and triangle. The consistent with the magnetic moment are 6.66{\mu}B, 5.54{\mu}B, 0.28{\mu}B, 1.04{\mu}B, 2.81{\mu}B, respectively. In addition, this work could pave the way for design new 2D metals electronic and magnetic properties.

Compression shortens the O:H nonbond and lengthens the H-O bond simultaneously via O:H-O Coulomb repulsion. The energy loss of the elongated H-O bond lowers the melting point., arXiv admin note: text overlap with arXiv:1501.06981

Unlike other unusual materials whose bonds contract under compression, the O:H nonbond undergoes contraction and the H-O bond elongation towards O:H and H-O length symmetry in water and ice. The energy drop of the H-O bond dictates the melting point Tm depression of ice. Once the pressure is relieved, the O:H-O bond fully recovers its initial state, resulting in Regelation., Continues arXiv:1501.04171 , arXiv:1501.00765, and "Hydrogen-bond relaxation dynamics: resolving mysteries of water ice", Coord. Chem. Rev., 2015. 285: 109-165

Because of the segmental specific-heat disparity of the hydrogen bond (O:H-O) and the Coulomb repulsion between oxygen ions, cooling elongates the O:H-O bond at freezing by stretching its containing angle and shortening the H-O bond with an association of larger O:H elongation, which makes ice less dense than water, allowing it to float.

Numerical reproduction of measurements, experimental evidence for skin super-solidity and hydrogen-bond memory clarified that Mpemba paradox integrates the heat emission-conduction-dissipation dynamics in the source-path-drain cycle system.

Molecular undercoordination induced O:H-O bond relaxation and dual polarization dictates the supersolid behavior of water skins interacting with other substances such as flowing in nanochannels, dancing of water droplets, floating of insects. The BOLS-NEP notion unifies the Wenzel-Cassie-Baxter models and explains controllable transition between hydrophobicity and hydrophilicity.

Molecular undercoordination shortens and stiffens the H-O bond but lengthens and softens the O:H nonbond simultaneously associated with O 1s energy entrapment and nonbonding electron dual polarization, which dictates behavior of water and ice dominated by undercoordinated molecules, such as droplets, bubbles, defects, skins, etc.

The elastic, less dense, polarized, and thermally stable supersolid skin lubricates ice. Molecular undercoordination shortens the H-O bond and lengthens the O:H nonbond through O-O repulsion, which is associated with low-frequency and high-magnitude of O:H vibration and a dual O-O polarization. The softer O:H springs attached with stronger molecular dipoles provide forces levitating objects sliding on ice, like Maglev or Hovercraft.

Complementing STM/S, U/XPS, and APECS, BOLS-NEP theory enabled ZPS (USA patent) distils atomistic, dynamic, local, and quantitative information of bond relaxation and associated energetics, localization, quantum entrapment, and polarization of electrons associated with adatoms, point defects, terrace edges, monolayer skins, nanocrystals, impurities, and interfaces. Distilled entitles dominate ubiquitously and will propel the ill-coordination Chemistry and Physics., This paper has been withdrawn by the author due to a crucial sign error in equations and figure captions

The mysterious nature and functionality of water and ice skins remain baffling to the community since 1859 when Farady firstly proposed liquid skin lubricating ice. Here we show the presence of supersolid phase that covers both water and ice using Raman spectroscopy measurements and quantum calculations. In the skin of two molecular layers thick, molecular undercoordination shortens the H-O bond by ~16% and lengthens the OH nonbond by ~25% through repulsion between electron pairs on adjacent O atoms, which depresses the density from 0.92 for bulk ice to 0.75 gcm-3. The O:H-O cooperative relaxation stiffens the H-O stretching phonon from 3200/3150 cm-1 to the same value of 3450 cm-1 and raises the melting temperature of both skins by up to ~310 K. Numerical derivatives on the viscosity and charge accumulation suggests that the elastic, polarized, and thermally stable supersolid phase makes the ice frictionless and water skin hydrophobic and ice like at room temperature.

Hydrogen-bond forms a pair of asymmetric, coupled, H-bridged oscillators with ultra-short-range interactions and memory. hydrogen bond cooperative relaxation and the associated binding electron entrapment and nonbonding electron polarization discriminate water and ice from other usual materials in the physical anomalies. As a strongly correlated fluctuating system, water prefers the statistically mean of tetrahedrally-coordinated structure with a supersolid skin that is elastic, polarized, ice like, hydrophobic, with 3/4 density., Comment: This paper has been withdrawn by the author due to a crucial sign error in equations and figure captions

Skins of water and ice share the same attribute of supersolidity characterized by the identical H-O vibration frequency of 3450 cm-1. Molecular undercoordination and inter-electron-pair repulsion shortens the H-O bond and lengthen the O:H nonbond, leading to a dual process of nonbonding electron polarization. This relaxation-polarization process enhances the dipole moment, elasticity,viscosity, thermal stability of these skins with 25% density loss, which is responsible for the hydrophobicity and toughness of water skin and for the slippery of ice., Comment: arXiv admin note: text overlap with arXiv:1401.8045

Inspired by responses to the work (arXiv:1310.6514), we solved the one-dimensional, nonlinear Fourier initial and boundary condition problem using the finite element method. Examination of all possible parameters reveals the following: 1. Hydrogen bond has memory effect to emit energy at a rate, or with a relaxation time, depending on initial energy storage. 2. Skin super-solidity creates gradients in thermal diffusion coefficient for heat conduction in liquid with the optimal skin-bulk ratio of 1.48. 3. Convection alone produces no such effect. 4. Mpemba effect happens only in the highly non-diabetic source-path-drain cycling system.

We demonstrate that the Mpemba paradox arises intrinsically from the release rate of energy initially stored in the covalent H-O part of the O:H-O bond in water albeit experimental conditions. Generally, heating raises the energy of a substance by lengthening and softening all bonds involved. However, the O:H nonbond in water follows actively the general rule of thermal expansion and drives the H-O covalent bond to relax oppositely in length and energy because of the inter-electron-electron pair coupling [J Phys Chem Lett 4, 2565 (2013); ibid 4, 3238 (2013)]. Heating stores energy into the H-O bond by shortening and stiffening it. Cooling the water as the source in a refrigerator as a drain, the H-O bond releases its energy at a rate that depends exponentially on the initially storage of energy, and therefore, Mpemba effect happens. This effect is formulated in terms of the relaxation time tau to represent all possible processes of energy loss. Consistency between predictions and measurements revealed that the tau drops exponentially intrinsically with the initial temperature of the water being cooled.

Raman spectroscopy examination of the 25 deg-C water freezing under compression revealed transition from 1.35 GPa to 0.86 GPa upon ice being formed at continued volume change. The transition is associated with a slight blue shift of the high-frequency phonon (omiga_H ~ 3120 cm-1) and creation of the low-frequency phonons (Omiga_L ~ 200 cm-1). In the liquid and in the solid phase, the increased pressure softens the Omiga_H and stiffens the Omida_L, which indicates the presence of the inter-electron-pair repulsion in both liquid and solid water.

We show that programmable heating and salting share the same effect on the frequency shift of the O:H and the H-O stretching phonons of the O:H-O hydrogen bond, which revealed that both heating and salting lengthens and softens the O:H bond and shortens and stiffens the H-O bond due to the weakening of the Coulomb repulsion between electron pairs of adjacent oxygen atoms. Understanding provides possible mechanism for the Hofmeister series and the detergent effect on cloth cleaning.

Consistency between theory predictions and measurements and calculations revealed that the skin of ice, containing water molecules with fewer than four neighbours, forms a supersolid phase that is highly polarized, elastic, hydrophobic, with ultra-low density and high thermal stability. The supersolidity of skin sliperizes ice., 2 figure 1 table

Combining the Lagrangian-Laplace mechanics and the known pressure dependence of the length-stiffness relaxation dynamics, we have determined the critical, yet often-overlooked, short-range interactions in the hydrogen bond of compressed ice. This approach has enabled determination of the force constant, cohesive energy, potential energy of the vdW and the covalent segment at each quasi-equilibrium state as well as their pressure dependence. Evidencing the essentiality of the inter-electron-pair Coulomb repulsion and the segmental strength disparity in determining the asymmetric H-bond relaxation dynamics and the anomalous properties of ice, results confirmed that compression shortens and stiffens the OH bond and meanwhile lengthens and softens the covalent bond.

The packing order of molecules and the distance between adjacent oxygen atoms (dOO) in water and ice are most basic yet puzzling. Here we present a scaling solution for this purpose based only on the mass density (gcm-3), (Equation) where dL is the length ({\AA}) of the O:H van der Waals bond and dH the H-O polar-covalent bond projecting on the O---O line. Validated by the measured proton symmetrization of compressed ice, dOO of water and ice, and dOO expansion at water surface, this solution confirms that the fluctuated, tetrahedrally-coordinated structure is unique for water ice.

Coulomb repulsion between the bonding electron pair in the H-O covalent bond (denoted by "-") and the nonbonding electron pair of O (":") and the specific-heat disparity between the O:H and the H-O segments of the entire hydrogen bond (O:H-O) are shown to determine the O:H-O bond angle-length-stiffness relaxation dynamics and the density anomalies of water and ice. The bonding part with relatively lower specific-heat is more easily activated by cooling, which serves as the "master" and contracts, while forcing the "slave" with higher specific-heat to elongate (via Coulomb repulsion) by different amounts. In the liquid and solid phases, the O:H van der Waals bond serves as the master and becomes significantly shorter and stiffer while the H-O bond becomes slightly longer and softer (phonon frequency is a measure of bond stiffness), resulting in an O:H-O cooling contraction and the seemingly "regular" process of cooling densification. In the water-ice transition phase, the master and the slave swap roles, thus resulting in an O:H-O elongation and volume expansion during freezing. In ice, the O--O distance is longer than it is in water, resulting in a lower density, so that ice floats., under review

The interplay between intra-molecular H-O covalent bond contraction, due to molecular under-coordination, and inter-molecular O:H expansion, due to inter-electron pair Coulomb repulsion, has been shown to be the source of the anomalous behavior of under-coordinated water molecules in nanoclusters and in the surfaces of water. The shortening of the H-O bond raises the local density of bonding electrons, which in turn polarizes the lone pairs of electrons on oxygen. The stiffening of the H-O bond increases the magnitude of O1s binding energy shift, causes the blueshift of the H-O phonon frequencies, and furthermore, elevates the melting point of molecular clusters and ultrathin films of water, which gives rise to their ice-like behavior at room temperature. At the same time, the elongation of the entire O:H-O bond polarizes and enlarges the under-coordinated H$_2$O molecules., Comment: under review

The study on the relationship between the spheres and voids in packing system suggests that the edge effect at the interface between the container and the particles is an important factor lowering the packing ratio. To pack spheres in a container with high packing ratio, an optimized sphere size and an optimized sequence of sphere sizes exist for the packing of single-sized and multi-sized spheres, respectively. We suggest that the concepts of volume and contact should be clearly defined for the packing problem in specific scale.

Coulomb repulsion between the unevenly-bounded bonding "-" and nonbonding ":" electron pairs in the "O2- : H+/p-O2-" hydrogen-bond is found to originate the anomalies of low-compressibility, phonon relaxation dynamics, proton symmetrization in the hydrogen-bond, and the change of the critical temperature for the VIII-VII phase transition of ice under compression. The resultant force of the compression, the repulsion, and the uneven binding strength of the electron pairs make the softer intermolecular "O2- : H+/p" nonbonding lone pair be highly compressed and stiffened but the stiffer intramolecular "H+/p-O2-" bond be elongated and softened. Consequently, the softer nonbond phonons (< 400 cm-1) are stiffened and the stiffer bond phonons (> 3000 cm-1) are softened upon compression. The nonbond compression and the real bond elongation results in the O2--H+/p : O2- symmetrization and the low compressibility of ice. Findings should form the starting point to unveil the physical anomalies of H2O under various stimuli., in sequence with arxiv.org/abs/1109.3958: H2O upon cooling from 298 to 98 K

A combination of the extended Ice Rule of Pauling, Raman spectroscopy, and molecular dynamics calculations has enabled us to clarify the bonding origin of the anomalous volume expansion, Raman phonon relaxation, and the stiffness and fragility of H2O upon frozen. We found that the initially shorter-and-stronger intramolecular "H+/p-O2-" bond follows the regular rule of cooling-contraction while the initially longer-and-weaker intermolecular "O2- : H+/p" nonbond turns to be even longer yet stiffer in the "O2- : H+/p-O2-" hydrogen-bond of H2O upon frozen, as a consequence of the polarization and Coulomb repulsion between the unevenly-bounded bonding and nonbonding electron pairs. The elongation of the nonbond and the polarization of the nonbonding lone pair are responsible, respectively, for the volume expansion and the stiffness and the fragility of ice. Findings should form important impact to the understanding of the physical anomalies of H2O under other stimuli such as pressure and confinement.

A zone-resolved photoelectron spectroscopy (ZPS) has enabled us to gain the local and quantitative information and hence confirm our theoretical expectations on the bonding and electronic dynamics at graphite skin with and without atomic vacancy defects. The ZPS study has revealed: i) the 1s energy level of an isolated carbon atom is located at 282.57 eV, which shifts by 1.32 eV deeper upon diamond bulk formation; ii) the graphite surface bonds contract by 18% with 165% gain in energy compared with the C-C bond in the bulk diamond; the surface C 1s energy shifts 2.08 eV deeper from the 1s level of an isolated carbon atom; and iii) the defect bonds are ~26% shorter and 215% stronger with the binding energy shift of ~2.85 eV. An additional polarization peak centered at 1.28 eV below the C 1s level presents when the vacancy is formed. Associated with the scanning tunneling microscopy/spectroscopy observations and density functional theory calculations, the ZPS measurements clarify, for the first time, that the graphitic Dirac-Fermi polarons at atomic vacancy or graphene zigzag edge arise from the polarization of the unpaired dangling-bond electrons by the undercoordination-induced local densification and quantum entrapment of the bonding electrons.

An effective yet simple means disclosed herewith has allowed us to gain the atomistic, local, and quantitative information of bonds and electrons at sites surrounding undercoordinated atoms, complementing the scanning tunneling microscopy/spectroscopy and photoelectron spectroscopy (XPS). Examining Rh and Pt surfaces with and without adatoms and graphite surface with and without atomic vacancies, we confirmed that: i) bonds between undercoordinated atoms become shorter and stronger; ii) subjective polarization happens to the valence electrons of defects or adatoms by the densely entrapped bonding electrons, which in turn screens and splits the crystal field and hence the core band of the specimen.

We present a simple approach for purifying graphite surface and vacancy states using an angle-resolved x-ray photoelectron residual spectroscopy (XPS). Complementing the discoveries of Ugeda et al [Phys Rev Lett 104, 096804 (2010)], outcomes conform the BOLS theory [Sun, Prog Solid State Chem 35, 1-159 (2007)] expectation and the recent findings that the shorter and stronger bonds between undercoordinated atoms induce local strain and quantum potential depression with an association of local densification of energy and core electrons. The shorter atomic distance and the densely and deeply trapped bonding and core charges polarize in turn the unpaired pi-electrons nearby vacancy, giving rise to the high protrusions and the Dirac EF states as observed. The quantum trap depression and the screening due to the polarized EF states split the crystal potential and hence the extra XPRS C 1s states., Comment: 13 draft pages, 3 figures

An analytical solution has been developed clarifying that the thermally driven elastic softening of crystals can be directly related to the length and strength of the representative bonds of the crystal and to the response of the bonding identities to the change of temperature. Reproduction of the experimental results Ag, Au, MgO, Mg2SO4, Al2O3, and KCl derived mean atomic cohesive energy of the specimen may evidence the validity of the proposed approach without involving parameters using in classical thermodynamics.

It has long been puzzling regarding the mechanism behind the nonlinearity of lattice thermal expansion at low temperatures despite modeling considerations from various perspectives in classical or quantum approximations. An analytical solution in terms of local bond average is presented herewith showing that the thermal expansion coefficient follows closely the specific heat of Debye approximation without the involvement of mode Gruneisen constant or the bulk modulus. Matching predictions to experimental observations using the Debye temperature and the atomic cohesive energy as input evidences that the current approach may represent the true situation of temperature induced lattice expansion though the exact form of phonon density of states need to be considered for further refinement.

Molecular dynamics calculations of the vibrational behavior of atoms in a Lennard-Jones 147-atom cluster revealed that the relaxation and the stability of the collective vibration of atoms in the cluster depend on the extent of the mechanical disturbance. A relatively larger-scale perturbation will cause a faster decay of the vibration magnitude, the potential and the kinetic energy compared to the vibration stimulated by a small-scale stimulus.

In order to gain advanced understanding of the kinetics and dynamics of C, N, and O reacting with a solid surface, it is necessary to consider the reaction from the perspectives of bond formation, bond dissociation, bond relaxation, bond vibration, and the associated charge redistribution and polarization and the energetic response of the involved atoms and valence electrons. The sp-orbital hybridization is found necessary for these concerned reactions associated with strongly anisotropic bonding and valence identities and the localized energy states of bonding pairs, nonbonding lone pairs, and the lone pair induced antibonding dipoles, as well as the hydrogen bond like and C-H bond like states, which could unify the observations using atomistic microscopy, crystallography, electronic spectroscopy, vibronic spectroscopy, and thermal desorption spectroscopy and provide guidelines for materials design., Book Chapter (invited)

Molecular dynamics calculations of the fluctuation of bond vibration revealed the shell-resolved kinetics of surface melting of closed-shelled cluster containing 147atoms with Lennard-Jones type interaction. It is found that the surface melting is imitated by the migrating of the vertex atoms and the melting process can be divided into three major stages, i.e., vertex migrating, surface melting, and general melting. Although the melting process of the LJ147 cluster could be divided into discrete stages of shell-by-shell surface melting, in general, there is still a continuous process of melting from the surface to the core interior.

It is expected that atomic vacancies or nanometric cavities reduce the number of chemical bonds of nearby atoms and hence the strength of a voided solid. However, the hardness of a porous specimen does not always follow this simple picture of coordination counting. An introduction of a certain amount of atomic vacancies or nanocavities could, instead, enhance the mechanical strength of the porous specimen. Understanding the mechanism behind the intriguing observations remains yet a high challenge. Here we show with analytical expressions that the shortened and strengthened bonds between the under-coordinated atoms and the associated local strain and energy trapping [Sun, Prog Solid State Chem 35, 1-159 (2007)] in the negatively curved surface skins dominate the observed nanocavity hardening. Agreement between predictions and the experimentally observed size-dependence of mechanical strength of some nanoporous materials evidences for the proposed mechanism.

Molecular dynamics calculations revealed that the temperature of operation and the applied tensile force (f) determine not only the kinetics but also the mode and duration of Au nanowire breaking. In the tensile force range of 0.018 and 0.1 nN/atom, structure transformation of the wire occurs prior to breaking at random positions. The gold wire breaks abruptly when the f is stronger than 0.1nN/atom but no rupture occurs at all when the f is weaker than 0.018 nN/atom. At higher temperatures and under stronger tensile forces, the wire breaks even faster.

Incorporating the bond-order-length-strength correlation mechanism [Sun CQ, Prog Solid State Chem 35, 1 -159 (2007)] and Borns criterion for melting [J. Chem. Phys. 7, 591(1939)] into the conventional Hall-Petch relationship has turned out an analytical expression for the size and temperature dependence of the mechanical strength of nanograins, known as the inverse Hall-Petch relationship (IHPR), that has long been a topic under debate regarding the possible mechanisms. Reproduction of the measured IHPR of Ni, NiP and TiO2 nanocrystals revealed that: (i) the size induced energy densification and cohesive energy loss of nanograins originates the IHPR that could be activated in the contact mode of plastic deformation detection; (ii) the competition between the inhibition of atomic dislocations, via the surface energy density gain and the strain work hardening, and the activation for dislocations through cohesive energy loss determine the entire IHPR profile of a specimen; (iii) the presence of a soft quasisolid phase is responsible for the size-induced softening and the superplasticity as well of nanostructures; (iv) the bond nature involved and the T/Tm ratio between the temperature of operating and the temperature of melting dictate the measured strongest sizes of a given specimen.

It has long been puzzling regarding the atomistic origin of the pressure-induced Raman phonon stiffening that generally follows a polynomial expression with coefficients needing physical indication. Here we show that an extension of the bond-order-length-strength (BOLS) correlation mechanism to the pressure domain has led to an analytical solution to connect the pressure-induced Raman phonon stiffening directly to the bonding identities of the specimen and the response of the bonding identities to the applied stimulus. It is found that the pressure-induced blue-shift of Raman phonons arises from the bond compression and energy storage exerted by the compressive stress. Agreement between predictions and experimental measurement leads to the detailed form for the polynomial coefficients, which offer an atomic understanding of the physical mechanism of the external pressure induced energy gain, thermally induced bond expansion as well as means of determining the mode atomic cohesive energy in a specimen.

Consistently atomistic understanding of the mechanism behind the intriguing behavior of low-dimensional systems including monatomic chains, hollow tubes, surface skins, nanocavities, nanowires, and nanograins has long been a high challenge. This article reports recent progress in this regard. A survey is presented and then is followed by analytical approaches in terms of local bond average (LBA) from the perspective of bonding energetics and its functional dependence on external stimuli of coordination environment and temperature change. It is shown that the measurable quantities of a specimen can be functionally correlated to the identities of the representative bonds and their responses to the external stimuli. It is understood that the shortened and strengthened bonds between the under-coordinated atoms and the associated local strain and energy trapping dictate intrinsically the mechanical behavior of systems with large portion of under-coordinated atoms. The thermal softening of a substance arises from thermally-induced bond expansion and lattice vibration that weakens the bonds through the internal energy increase. The competition between the energy-density-gain and the residual atomic cohesive-energy in the relaxed surface skin determines intrinsically the mechanical performance of a mesoscopic specimen, whereas competition between the activation and inhibition of atomic dislocations dominates extrinsically the yield strength of the specimen in plastic deformation., Comment: 156 pages and 50 figures

Extending the recently-developed bond-order-length-strength (BOLS) correlation mechanism [Sun CQ, Prog Solid State Chem 2007, 35, 1-159] to the pressure domain has led to atomistic insight into the phase stability of nanostructures under the varied stimuli of pressure and solid size. It turns out that the competition between the pressure-induced overheating (TC elevation) and the size-induced undercooling (TC depression) dominates the measured size trends of the pressure-induced phase transition. Reproduction of the measured size and pressure dependence of the phase stability for CdSe, Fe2O3, and SnO2 nanocrystals evidences the validity of the solution derived from the perspective of atomic cohesive energy and its response to the external stimulus., Comment: 13 pages and 3 figures. to be appeared in J Phys Chem C

It has been puzzling that the Raman optical modes shift to lower frequency (or termed as optical mode softening) associated with creation of Raman acoustic modes that shift to higher energy (or called as acoustic hardening) upon nanosolid formation and size reduction. Understandings of the mechanism behind the size-induced acoustic hardening and optic softening have been quite controversial. On the basis of the recent bond order-length-strength (BOLS) correlation [Phys. Rev. B 69 045105 (2004)], we show that the optical softening arises from atomic cohesive energy weakening of surface atoms and the acoustic mode hardening is predominated by intergrain interaction. Agreement between predictions and observations has been reached for Si, CdS, InP, TiO2, CeO2, and SnO2 nanostructures with elucidation of vibration frequency of the corresponding isolated dimers. Findings further evidence the impact of bond order loss to low-dimensional systems and the essentiality of the BOLS correlation in describing the behavior of nanostructures., 14 pages, 2 figures

Introduction bond-band-barrier (BOLS) correlation for the effect of electronic process of oxidation and the bond order-length-strengtrh (BOLS) correlation for the behaviour of nanostructures., 40 pages; 130 refs. 10 figure, to be published by John Wiley

This report presents consistent insight into the mechanism behind the unusual behavior of nitride compounds from the perspective of tetrahedron bond formation and its consequence on valence density of states. An extension of the recent bond-band-barrier (BBB) correlation mechanism for oxidation [Sun CQ, Prog Mater Sci 2003;48:521-685] to the electronic process of nitridation has led to the essentiality of sp-orbital hybridization for a nitrogen atom upon interacting with atoms in solid phase of arbitrary less-electronegative element. In the process of nitridation, a nitrogen atom forms a quasi-tetrahedron with surrounding host atoms through bonding and nonbonding interaction associated with production of electronic holes and antibonding dipoles, which add corresponding density of states to the valence band of the host. It is suggested that the valance alteration of the system takes the responsibility for the blue shift in photoluminescence, lowered work function for cold cathode field emission, corrosion and wear resistant, high elasticity, and magnetic modulation as well., 21 pages, Review, 12 figures, abd 76 references

Thermally stimulated process such as evaporation, phase transition, or solid-liquid transition of a solid consumes each a certain portion of the solid cohesive energy that is the sum of bond energy over all the coordinates of all the involved atoms. Generally, the critical temperatures for such processes drop with solid size, unless hetero capping or interfacial interaction becomes dominant, because of the increased portion of the lower-coordinated surface atoms [Sun et al., J. Phys. Chem. B108, 1080 (2004)]. It is intriguing, however, that the melting point (Tm) of a solid containing III-A or IV-A atoms oscillates with size (the Tm drops first and then rises as the solid size is reduced) and that the Tm of chemically capped nanosolid often increases with the inverse size. Here we show that bond nature evolution is essential for the selective nanosolids and at the junction interfaces, which is responsible for the superheating of the smallest nanosolids, chemically capped clusters, and junction interfaces that exhibit insulating nature with high mechanical strength., 18 pages; 4 figures, 80 references

This report deals with the correlation between the mechanical strength and thermal stability of systems extending from monatomic chains to surface skins and solids over the whole range of sizes with emphasis on the significance of atomic coordination imperfection. Derived solutions show that a competition between the bond order loss and the associated bond strength gain of the lower coordinated atoms dictate the thermo-mechanics of the low dimensional systems. Bond order loss lowers the atomic cohesive energy that determines the temperature of melting (Tm), or the activation energy for atomic dislocation, whereas bond strength gain enhances the energy density, or mechanical strength, in the surface skin. Therefore, the surface is harder at T << Tm whereas the surface becomes softer when the T approaches the surface Tm that is lower than the bulk due to bond order loss. Hence, the strained nanostructures are usually stiffer at low T whereas the harder skins melt easier. Quantitative information has been obtained about the bonding identities in metallic monatomic chains and carbon nanotubes. Solutions also enable us to reproduce the inverse Hall-Petch relationship with clarification of factors dominating the transition from hardening to softening in the nanometer regime., Review 42 pages, 12 figures 183 references