Search

Consistency between x-ray photoelectron spectroscopy measurements and density-function theory calculations confirms our bond order-length-strength notation-incorporated tight-binding theory predictions on the quantum entrapment of Si solid skin and atomic clusters. It has been revealed that bond-order deficiency shortens and strengthens the Si-Si bond, which results in the local densification and quantum entrapment of the core and valence electrons. Unifying Si clusters and Si(001) and (111) skins, this mechanism has led to quantification of the 2p binding energy of 96.089 eV for an isolated Si atom, and their bulk shifts of 2.461 eV. Findings evidence the significance of atomic undercoordination that is of great importance to device performance. [ABSTRACT FROM AUTHOR]

A sequential of concepts developed in the last decade has enabled a resolution to multiple anomalies of water ice and its low-dimensionality, particularly. Developed concepts include the coupled hydrogen bond (O:H–O) oscillator pair, segmental specific heat, three-body coupling potentials, quasisolidity, and supersolidity. Resolved anomalies include ice buoyancy, ice slipperiness, water skin toughness, supercooling and superheating at the nanoscale, etc. Evidence shows consistently that molecular undercoordination shortens the H–O bond and stiffens its phonon while undercoordination does the O:H nonbond contrastingly associated with strong lone pair ":" polarization, which endows the low-dimensional water ice with supersolidity. The supersolid phase is hydrophobic, less dense, viscoelastic, thermally more diffusive, and stable, having longer electron and phonon lifetime. The equal number of lone pairs and protons reserves the configuration and orientation of the coupled O:H–O bonds and restricts molecular rotation and proton hopping, which entitles water the simplest, ordered, tetrahedrally-coordinated, fluctuating molecular crystal covered with a supersolid skin. The O:H–O segmental cooperativity and specific-heat disparity form the soul dictate the extraordinary adaptivity, reactivity, recoverability, and sensitivity of water ice when subjecting to physical perturbation. It is recommended that the premise of "hydrogen bonding and electronic dynamics" would deepen the insight into the core physics and chemistry of water ice. [ABSTRACT FROM AUTHOR]

Aqueous charge injection in forms of electrons, protons, lone pairs, ions, and molecular dipoles by solvation is ubiquitously important to our health and life. Pursuing fine-resolution detection and consistent insight into solvation dynamics and solute capabilities has become an increasingly active subject. This treatise shows that charge injection by solvation mediates the O:H-O bonding network and properties of a solution through O:H formation, H↔H fragilization, O:⇔:O compression, electrostatic polarization, H2O dipolar shielding, solute-solute interaction, and undercoordinated H-O bond contraction. A combination of the hydrogen bond (O:H-O or HB with ':' being the electron lone pairs of oxygen) cooperativity notion and the differential phonon spectrometrics (DPS) has enabled quantitative information on the following: (i) the number fraction and phonon stiffness of HBs transiting from the mode of ordinary water to hydration; (ii) solute-solvent and solute-solute molecular nonbond interactions; and (iii) interdependence of skin stress, solution viscosity, molecular diffusivity, solvation thermodynamics, and critical pressures and temperatures for phase transitions. An examination of solvation dynamics has clarified the following: (i) the excessive protons create the H↔H or anti-HB point breaker to disrupt the acidic solution network and surface stress. (ii) The excessive lone pairs generate the O:⇔:O or super-HB point compressor to shorten the O:H nonbond but lengthen the H-O bond in H2O2 and basic solutions; yet, bond-order-deficiency shortens and stiffens the H-O bond due H2O2 and OH− solutes. (iii) Ions serve each as a charge center that aligns, clusters, stretches, and polarizes their neighboring HBs to form hydration shells. (iv) Solvation of alcohols, aldehydes, complex salts, carboxylic and formic acids, glycine, and sugars distorts the solute-solvent interface structures with the involvement of the anti-HB or the super-HB. Extending the knowledge and strategies to catalysis, solution-protein, drug-cell, liquid-solid, colloid-matrix interactions and molecular crystals would be even more fascinating and rewarding. [ABSTRACT FROM AUTHOR]

Incorporating the bond–order–length–strength correlation mechanism [C. Q. Sun, Prog. Solid State Chem.35, 1 (2007)] and Born's 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). Reproduction of the measured IHPR of Ni, NiP, and TiO2 nanocrystals revealed that: (i) the competition between the size-induced energy–density gain and atomic cohesive energy loss in the surface skins of nanograins originate from the IHPR; (ii) the competition between the activation and inhibition of atomic dislocations motion activate the entire IHPR behavior; (iii) 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; (iv) a quasimolten phase present before melting determines the size-induced softening and the superplasticity of nanostructures. [ABSTRACT FROM AUTHOR]

Abstract: The electronic processes of Cu(Ag, V, Rh)(001) surface oxidation are comparatively analyzed based on the recent ‘chemical bond–valence band–potential barrier’ (BBB) correlation mechanism [C.Q. Sun, Prog. Mater. Sci. 48, 521–685 (2003)], which allows reaction formulae for all the observed phases with identification of individual atomic valence and the binding kinetics at the surfaces with the same geometry. It is consistently understood that the forming kinetics of the primary oxide tetrahedron and its derivative on the valence density-of-states (DOS) are intrinsically common for all these analyzed systems, though the patterns of observation in terms of morphology and crystallography vary from situation to situation. However, the lattice size and electronegativity of the host surfaces determine extrinsically the site selectivity of the oxygen, the order of bond formation and the orientation of the oxide tetrahedron. [Copyright &y& Elsevier]

Consistent insight into the size-enhanced E4f-level shift and the size-suppressed melting point of Au nanosolids has been obtained based on the bond order-length-strength (BOLS) correlation mechanism [Sun et al., Acta Mater. 51 (2003) 4631]. Consistency between theory predictions and observations reveals that the atomic-coordination number (CN)-imperfection induced bond contraction and the associated bond energy increase dictate these changes. The increase of binding energy density per unit volume in the relaxed surface region perturbs the Hamiltonian that determines the core-level shift; the decrease of atomic cohesive energy (a product of atomic CN and the single bond energy) determines the thermal energy required for melting. Extending the knowledge to the lower end of the size limit suggests that the metallic bond in the gold monatomic-chain contracts by ∼30% associated with ∼43% magnitude rise of the bond energy. The crystal binding intensity contributing from all the atoms in the solid to the Au-E4f electrons in the bulk is determined to be −2.87 eV. [Copyright &y& Elsevier]

This report features the recent progress in understanding the behaviour of atoms and valence electrons involved in the process of oxidation, and some technological development driven by the new knowledge. It is initiated and verified that a chemical bond contracts spontaneously at a surface associated with magnitude rise of the bond energy due to the coordination imperfection and that an oxygen atom hybridizes its sp orbitals upon reacting with a solid surface. The former leads to the bond order–length–strength (BOLS) correlation for the physical aspect of a surface and a nano-solid and the latter to a bond–band–barrier (BBB) correlation for chemical reaction. In the process of oxidation, non-bonding lone pairs, anti-bonding dipoles and hydrogen-like bonds are involved, which add corresponding density-of-states (DOS) features to the valence band of the host. Bond forming also alters the sizes and valencies of the involved atoms and causes a collective dislocation of these atoms, which corrugate the morphology or the potential barrier of the surface. Based on the above premises, the oxidation of the low-index surfaces of transition metals Cu, Co, Ag and V, noble metals Rh, Ru, and Pd and non-metallic diamond has been consistently analyzed. Identities probed with various techniques, such as STM, LEED, XRD, STS, PES, TDS, EELS and Raman, have been systematically defined in terms of atomic valencies, bond geometry, valence DOS, bond strength and bond forming kinetics. It is understood that formation of the basic oxide tetrahedron, and consequently, the four discrete stages of bond forming kinetics and the oxygen-derived DOS features, are intrinsically common for all the analyzed systems though the patterns of observations may vary from situation to situation. What differs one oxide surface from another in observations are: (i) the site selectivity of the oxygen adsorbate, (ii) the order of the ionic bond formation and, (iii) the orientation of the tetrahedron at the host surfaces. The valencies of oxygen, the scale and geometrical orientation of the host lattice and the electronegativity of the host elements determine these specific differences extrinsically. Extending the premise of sp-orbital hybridization to the reactions of (C, N)–Ni(001) surfaces has led to a novel approach neutralizing the diamond–metal interfacial stress and hence strengthening the diamond–metal adhesion substantially. The BOLS correlation has provided consistent insight into the shape-and-size dependence of a number of properties for nano-solids. The BBB correlation has led to new findings in designing and fabricating materials for photoluminescence, electron emission and ultrahigh elasticity, etc. [Copyright &y& Elsevier]

A new description of bonding and band-forming is presented for the nature and dynamics of O-Rh(111) and O-Ru(0001) surface bonding and its consequences on the behavior of atoms and electrons at the surfaces. The sp-orbital hybridization and electron transportation define that oxygen retains inside the hcp hollow site throughout the course of reaction in which O[sup -1] forms and then O[sup -2]-hybrid follows with production of nonbonding lone pairs and the lone-pair induced antibonding dipoles. Consequently, the valence band and surface morphology are modified with the corresponding features, and the radial and pairing-row reconstruction arises in the corresponding phases. [ABSTRACT FROM AUTHOR]

Correlation between chemical bonds, energy bands, and the corresponding properties of oxides and nitrides is established. It is proposed that an oxygen or nitrogen atom can hybridize and form a tetrahedron with its four neighbors through bonding orbitals and nonbonding lone pairs. As a result, the energy states of the host material are modified with four additional features, namely, sp[sup 3]-hybrid bonding, nonbonding (lone pair), antibonding (dipole), and hole states. Therefore, oxygen and nitrogen possess the special ability of not only enlarging the band gap by hole production but also adding an antibonding subband above the Fermi level. © 1998 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Abstract: The 2p3/2 core-level binding energy (BE) shifts of Fe surface and Fe nanoparticles have been analyzed by considering the bond order-length-strength (BOLS) correlation mechanism in decomposition of the X-ray photoelectron spectrum (XPS). It turns out that the Fe 2p3/2 BE shifts positively by 2.17eV from the atomic value of 704.52eV to the bulk value of 706.69eV and that a further 0.32 and 0.16eV positive shift occurs, respectively, to the top and the second atomic layers. Consistency between BOLS predictions and the measured size dependence of BE shift clarifies the dominance of the broken-bond-induced local strain and quantum trapping in perturbing the Hamiltonian and hence the positive shift of the 2p3/2 BE of Fe surface and Fe nanostructures. [Copyright &y& Elsevier]

We have examined the atomic coordination effect on the local bond strain and the 3p core-level shift of K(1 1 0) skin and nanoclusters using a combination of the bond order–length–strength correlation notion, tight-binding approach, density functional theory calculations, and photoelectron spectroscopy measurements. It turns out that: (i) the 3p core-level shifts from 15.595 ± 0.003 eV for an isolated K atom by 2.758 eV to the bulk value of 18.353 eV; (ii) the effective atomic coordination number reduces from the bulk value of 12 to 3.93 for the first layer and to 5.81 for the second layer of K(1 1 0) skin associated with the local lattice strain of 12.76%, a binding energy density 72.67%, and atomic cohesive energy −62.46% for the skin; and (iii) K cluster size reduction lowers the effective atomic coordination number and enhances further the skin electronic attribution. Results have revealed that the 3p core-level shifts of K(1 1 0) and nanoclusters originate from perturbation of the Hamiltonian by under-coordination induced charge densification and quantum entrapment. [ABSTRACT FROM AUTHOR]

Consistency between density functional theory calculations and photoelectron spectroscopy measurements confirmed our predications on the undercoordination-induced local bond relaxation and core level shift of Na and K clusters. It is clarified that the shorter and stronger bonds between under-coordinated atoms cause local densification and local potential well depression and shift the electron binding-energy accordingly. Numerical consistency turns out the energy levels for an isolated Na ( E 2p = 31.167 eV) and K ( E 3p = 18.034 eV) atoms and their respective bulk shifts of 2.401 eV and 2.754 eV, which is beyond the scope of conventional approaches. This strategy has also resulted in quantification of the local bond length, bond energy, binding energy density, and atomic cohesive energy associated with the undercoordinated atoms. [ABSTRACT FROM AUTHOR]

Numerical reproduction of the measured 4 f 7/2 energy shift of Ir(1 0 0), (1 1 1), and (2 1 0) solid skins turns out the following: (i) the 4 f 7/2 level of an isolated Ir atom shifts from 56.367 eV to 60.332 eV by 3.965 eV upon bulk formation; (ii) the local energy density increases by up to 130% and the atomic cohesive energy decreases by 70% in the skin region compared with the bulk values. Numerical match to observation of the temperature dependent energy shift derives the Debye temperature that varies from 285.2 K (Surface) to 315.2 K (Bulk). We clarified that the shorter and stronger bonds between under-coordinated atoms cause local densification and quantum entrapment of electron binding energy, which perturbs the Hamiltonian and the core shifts in the skin region. [ABSTRACT FROM AUTHOR]

Incorporating the tight-binding theory and the bond order–length–strength(BOLS) correlation into the X-ray photoelectron spectra of Ag(111)and (100) surfaces and the Auger electron spectra of Ag nanoparticlesdeposited on Al2O3and CeO2substrateshas led to quantitative information of the 3d5/2and thevalence binding energies of an isolated Ag atom and their shifts uponbulk, defect, surface, and nanocrystal formation. It is clarifiedthat the globally positive energy shifts originate from the undercoordination-inducedGoldschmidt–Pauling bond contraction and the associated localquantum entrapment and the heterocoordination-induced bond naturealteration at the particle–substrate interfaces. Perturbationto the Hamiltonian by atomic ill-coordination dictates the energyshift that is proportional to the bond energy at equilibrium. Theoreticalreproduction of the measured spectroscopic data derived that the 3d5/2energy of an isolated Ag atom shifts from 363.02 to 367.65eV and the valence band center from 0.36 to 8.32 eV upon bulk formation.The extended Wagner plots revealed the coefficients of valence rechargingand potential screening to be 1.21 and 1.56 for Ag interacting withAl2O3substrate and 1.15 and 1.50 for Ag withCeO2, respectively. Exercises exemplify the enhanced capabilitiesof XPS and AES in determining quantitative information regarding theevolution of the local bond length, bond energy, binding energy density,and atomic cohesive energy, with the coordination and chemical environment. [ABSTRACT FROM AUTHOR]

The article focuses on the results of the formulation, correlation, clarification, and quantification of the behavior of zinc oxide (ZnO) for five years. It states the exercises undertaken for the bond-band correlation were based on three frameworks namely bond-order-length-strength (BOLS) correlation, nonbonding electron polarization (NEP), and local bond averaging (LBA) method. It explores the catalytic performance, dilute magnetism, and superhydrophobicity of ZnO.