Equalized Electronegativity Based on the Valence Electrons and Its Application

We take the contribution of all valence electrons into consideration and propose a new valence electrons equilibration method to calculate the equalized electronegativity including molecular electronegativity, group electronegativity, and atomic charge. The ionization potential of alkanes and mono-substituted alkanes, the chemical shift of 1H NMR, and the gas phase proton affinity of aliphatic amines, alcohols, and ethers were estimated. All the expressions have good correlations. Moreover, the Sanderson method and Bratsch method were modified on the basis of the valence electrons equilibration theory. The modified Sanderson method and modified Bratsch method are more effective than their original methods to estimate these properties.

Effects of Nb and Si on densities of valence electrons in bulk and defects of Fe_3Al alloys

Positron lifetime measurements have been performed in binary Fe3Al and Fe3Al doping with Nb or Si alloys. The densities of valence electrons of the bulk and microdefects in all tested samples have been calculated by using the positron lifetime parameters. Density of valence electron is low in the bulk of Fe3Al alloy. It indicates that, the 3d electrons in a Fe atom have strong-localized properties and tend to form covalent bonds with Al atoms, and the bonding nature in Fe3Al is a mixture of metallic and covalent bonds. The density of valence electron is very low in the defects of Fe3Al grain boundary, which makes the bonding cohesion in grain boundary quite weak. The addition of Si to Fe3Al gives rise to the decrease of the densities of valence electrons in the bulk and the grain boundary thus the metallic bonding cohesion. This makes the alloy more brittle. The addition of Nb to Fe3Al results in the decrease of the ordering energy of the alloy and increases the density of valence electron and the bonding cohesion of the grain boundary. However, since the radius of Nb atom is larger than that of Fe atom, when Nb atoms substitute for Fe atoms, they will distort the lattice and enlarge the volume of the lattice, which decreases the density of valence electron and the cohesion of metallic bond in the bulk of the alloy.

Effect of Valence Electron Structure on Temper Process and Hardness of the Supersaturated Carburized Layer

By measuring the hardness of carburized layer of a new type supersaturated carburizing steel （35Cr3SiMnMoV） at different temper temperature for 2 h, the relationship curve between the carburized layer hardness and the temper temperature is established. The result indicates that the hardness goes down firstly, then up and down, just like a wave consistent with the temperature increase. A secondary hardening peak appears at 570 ℃ or so. Based on Empirical Election Theory （EET） of Solids and Molecules, the valence electron structures （VESs） containing α-Fe-C, α-Fe-C-Me segregation structure units and carbide are calculated. The laws of temper process and hardness change with the temper temperature are explained, and the fact that reconstruction of θ-Fe3C is prior to that of special carbide at high tempering is analyzed with the phase structure formation factor, S, being taken into consideration. Therefore, the laws of temper process and hardness change of supersaturated carburized layer at different temper temperature can be traced back to valence electron structure （VES） level of alloy phase.

Effects of 4f Electron Characteristics and Alternation Valence of Rare Earths on Photosynthesis: Regulating Distribution of Energy and Activities of Spinach Chloroplast

Chloroplasts were isolated from spinach treated with taCl3, CeCl3, and NdCl3. Because of owning 4f electron characteristics and alternation valence, Ce treatment presented the highest enhancement in light absorption, energy transfer from LHC Ⅱ to PS Ⅱ, excitation energy distribution from PS Ⅰ to PS Ⅱ, and fluorescence quantum yield around 680 nm. Compared with Ce treatment, Nd treatment resulted in relatively lower enhancement in these physiological indices, as Nd did not have alternation valence. La treatment presented the lowest enhancement, as La did not have either 4f electron or alternation valence. The increase in activities of whole chain electron transport, PS ⅡDCPIP photoreduction, and oxygen evolution of chloroplasts was of the following order： Ce〉Nd 〉La〉 control. However, the photoreduction activities of spinach PS I almost did not change with La, Ce, or Nd treatments. The results suggested that 4f electron characteristics and alternation valence of rare earths had a close relationship with photosynthesis improvement.

A Valence Electron Structure Criterion of Ionic Conductivity of Sr- and Mg-doped LaGaO_3 Ceramics

The valence electron structures of Sr- and Mg-doped LaGaO3 ceramics with different compositions were calculated by Empirical Electron Theory of Solids and Molecules （EET）. A criterion for the ionic conductivity was proposed, i.e. the 1/（nAnB） increases with increasing the ionic conductivity when x or y〈20% （in molar fraction）.

Analysis of Valence Electron Structure of RE in Solid Solution in Medium and Low Carbon Steel

According to EET theory, the valence electron structures of RE in the solid solution of austenite, pearlite and martensite were calculated. The influence of RE in solid solution on phase transformation of pearlite and recrystallization of martensite was explained by the valence electron structure data of phases. Calculating results indicate that C element is favorite to enhance the number of RE in the solid solution. RE in the solute solution shortens the incubation period of proeutectoid ferrite, increases its quantity and carbon content, decreases the quantity of pearlite and thickness of its lamellas and lamellar spacing, then the strength and hardness of pearlite are improved and granular pearlite can be obtained. RE dissolved in martensite intensifies martensite, enhances tempering stability of martensite, increases its recrystallization temperature and prolongs the holding time needed during tempering.

Study Segregation of Alloying Elements in Continuous Casting Slab with Valence Electron Structure

By calculating the electron structures of the phases that phosphor, sulfur and alloying elements dissolving inγ-Fe, the reason why alloying elements can bring centerline segregation in continuous casting slab (CCS) with nA, the number of electrons on the strongest covalent bonds, and the structure formation factor S were investigated, and an electron structural criterion to control and to eliminate the centerline segregation was advanced. Basing on this, the electron structures of a part of rare earth phosphides and sulfides are calculated, the physical mechanism that rare earth elements can control the segregation of phosphor and sulfur is analyzed, and the criterion is well verified.

ELECTRON TRANSFER AND PHOTOCHEMICAL VALENCE ISOMERIZATION IN ANTHRACENE AND NORBORNADIENE SYSTEMS

To harvest the sun light and to promote the amount of energy stored,a new binary compound which links a sensitizer(electron donor), anthracene,and substrate(electron acceptor),norbornadiene,in a non- conjugated manner without increase in molecular weight was synthesized.The inter-and intramolecular photosensitized isomerization and the mechanism were studied.

Valence electron structures dependences of structural stability and properties of REX_(3)(RE=rare earth;X=In,Tl)and RE(In,Co)3 alloys

Intermetallic compounds REIn3(RE=rare earth)have attracted much attention due to their unique characteristics:crystal field effect,Kondo effect,superconductivity,heavy fermion,and antiferromagnetism,and their cobalt diluted alloys exhibit the ferromagnetic half-metallic characteristics at room temperature.In this study,an empirical electron theory(EET)is employed to investigate systemically the valence electronic structure,the thermal and magnetic properties of REX_(3) and their cobalt diluted alloys for revealing the mechanism of physical properties.The calculated bond length,melting point,and magnetic moment match the experimental ones very well.The study reveals that structural stability and physical properties of REX_(3) and their cobalt dilute alloys are strongly related to their valence electron structures.It is suggested that the structural stability and cohesive energy depend upon the covalent electron,the melting point is modulated by covalent electron pair,and the magnetic moment is originated from 3d magnetic electron.The ferromagnetic characteristics of Co-diluted REIn3 alloys is originated from the introduction of strong ferromagnetic Co atom,but,a competition is caused between the electron transition from valence electron to magnetic electron on d orbit and its reversal electron transformation with increasing the content of cobalt,which results in the formations of diluted magnetic Gd(In,Co)3 alloy with minor amount of cobalt and strong magnetic Nd(In,Co)3 alloy with doping more Co atoms.

DETERMINATION AND APPLICATION OF LARSON-MILLER PARAMETER FOR HEAT RESISTANT STEEL 12CrlMoV AND 15CrMo

Based on the analysis and processing on relative empirical formula and data, C-values in Larson-Miller (P) expression, P= T(C + Igt), have determined for pearlitic heat resistant steel 12Cr1MoV and 15CrMo(20.62 and 20.30). The simulation experiments of high temperature aging, heated from 1.5 to 873 hours, have been designed and performed for its verification. And in combination with published information and the present nearly quantitative works, it has further been verified that both the degradations of microstructures and mechanical properties show a good accuracy and practicability using the Larson-Miller parameter with the present determined C-values. Finally, the effects of carbon content on C-value are analyzed by the empirical electron theory of solids and molecules (EET).

Differences of grain-refining effect of Sc and Ti additions in aluminum by empirical electron theory analysis

The differences of grain-refining effect between Sc and Ti additions in aluminum,which cannot be substantially explained by traditional theories,were carefully studied.The empirical electron theory(EET) of solids and molecules was employed to calculate the valence electron structures(VES) of Al3Ti and Al3Sc.The conclusions can be drawn that,in the two alloys Al-Ti and Al-Sc,the different valence electron structures of Al3Ti and Al3Sc and the consequent differences of growth habit of the two particles,and the different interfacial electron density between particles and matrix fundamentally lead to the differences of grain-refining effect between Sc and Ti additions on aluminum and make Sr the better grain-refiner of aluminum.

Correlation between electronic structure and energy band in Eu-doped CuInTe_2 semiconductor compound with chalcopyrite structure

The Eu-doped Cu（In, Eu）Te2 semiconductors with chalcopyrite structures are promising materials for their applications in the absorption layer for thin-film solar cells due to their wider band-gaps and better optical properties than those of CuInTe2. In this paper, the Eu-doped CuInTe2 （CuIn1-xEuxTe2, x = 0, 0.1, 0.2, 0.3） are studied systemically based on the empirical electron theory （EET）. The studies cover crystal structures, bonding regularities, cohesive energies, energy levels, and valence electron structures. The theoretical values fit the experimental results very well. The physical mechanism of a broadened band-gap induced by Eu doping into CuInTe2 is the transitions between different hybridization energy levels induced by electron hopping between s and d orbitals and the transformations from the lattice electrons to valence electrons for Cu and In ions. The research results reveal that the photovoltaic effect induces the increase of lattice electrons of In and causes the electric resistivity to decrease. The Eu doping into CuInTe2 mainly influences the transition between different hybridization energy levels for Cu atoms, which shows that the 3d electron numbers of Cu atoms change before and after Eu doping. In single phase CuIn1-xEuxTe2, the number of valence electrons changes regularly with increasing Eu content, and the calculated band gap Eg also increases, which implies that the optical properties of Eu-doped CuIn1-xEuxTe2 are improved.

Electrical conductivity of Cu-Li alloys

The electrical conductivity of Cu-Li alloys was studied. And the distribution of electrons near Fermi surface was detected by synchrotron radiation instrument. The results show that the electrical conductivity of Cu-Li alloys decreases from 5.22 X 10(-9) S/m to 3.69 X 10(-9) S/m with the increase of Li content. Li can decrease the oxygen, sulfur and other impurities content in commercial Cu, but Li dissolved in Cu lattice leads to distortion of Cu lattice from 0.005%-0.050%, affects the valence band of Cu, increases the binding energy of surface electron, and decreases the electron density of Fermi surface simultaneously. So the electrical conductivity decreases gradually with the increase of Li content.

Calculations of stability of alloyed cementite from valance electron structure

Based on the empirical electronic theory of solids and molecules （EET）, the actual model for unit cell of cementite （0-FeaC） was built and the valence electron structures （VES） of cementite with specified site and a number of Fe atoms substituted by alloying atoms of M （ M=Cr, V, W, Mo, Mn ） were computed by statistical method. By defining P as the stability factor, the stability of alloyed cementite with different numbers and sites of Fe atoms substituted by M was calculated. Calculation results show that the density of lattice electrons, the symmetry of distribution of covalent electron pairs and bond energy have huge influence on the stability of alloyed cementite. It is more stable as M substitutes for FeE than for Fe1. The alloyed cementite is the most stable when Cr, Mo, W and V substitute for 2 atoms of Fe2 at the sites of Nos. 2 and 3 （or No. 6 and No. 7）. The stability of alloyed cementite decreases gradually as being substitutional doped by W, Cr, V, Mo and Mn.

A New hcp Phase Formed in the Ni-Nb System during Ion-beam-assisted Deposition

The Ni80Nb20 films were prepared by ion beam assisted deposition (IBAD) with various Ar+ ion energies. A phase evolution of fcc→amorphous→Ni+Nb→Ni+hcp was observed with the increasing of ion beam energy from 2 keV to 8 keV. When bombarded by Ar+ ions of 8 keV during deposition, a new crystalline phase with hcp structure was obtained, of which the lattice parameters are a=0.286 nm and c=0.483 nm, different from those of the similar A3B-type hcp phase previously reported. The experimental results were discussed in terms of thermodynamics and restricted kinetic conditions in the far-from-equilibrium process of IBAD. The formation of hep phase may also be related to the valence electron effect.

Tuning the electron structure enables the NiZn alloy for CO_(2) electroreduction to formate

Formate is an important liquid chemical,which can be produced by electrocatalytic carbon dioxide reduction reaction(CO_(2) RR).Most of the metal catalysts for CO_(2) RR to formate are toxic or noble metals,such as Cd,Hg,Pb and Pd,leading to the environmental pollution or increased production costs.Herein,we develop an environmentally friendly and low-cost NiZn alloy catalyst for CO_(2) RR to formate.The X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM) confirm the alloy structure of the prepared NiZn catalyst. As for a catalyst for CO_(2) RR,the NiZn alloy exhibits the FE_(HCOO)^(-)(Faraday efficiency of HCOO^(-)) of 36±0.7% at-0.9 V vs.RHE in 0.1 M KHCO_(3), and remarkable stability for 40,000 s at-0.8,-0.9,-1.0 and-1.1 V vs.RHE,respectively.Theoretical calculation results indicate that the NiZn alloy exhibits the middle valence electron structure between the Zn and Ni metal,resulting in the favorable pathway for HCOOH formation but unfavorable for the hydrogen evolution reaction and CO production.The Ultraviolet Photoelectron Spectroscopy results verify the modulated valence electron structure for NiZn alloy as compared to Ni and Zn,consistent with the theoretical calculation results.This work provides new insights into design of alloy catalysts for CO_(2) RR to formate.

EFFECT OF HETEROGENEOUS DISTRIBUTION OF C AND ALLOYING ELEMENTS ONγ/α′TRANSFORMATION IN A Fe-Mn-Cr-C ALLOY

The heterogeneous distribution of C and metallic alloying elements as well as the phase com- position changes before and after cold deformation of an Fe-Mn-Cr-C alloy have been stu- died by the use of Mssbauer spectroscopy.The austenites without and with C and metallic alloying elements are found in the alloy in as-solid solution state.While the martensites with- out and with C and alloying elements may be induced by cold deformation.The transforma- tion from austenite to martensite in the alloy is confirmed via theoretical computation and ex- periments to be controlled by the number of covalent electron pairs forming covalent bond in austenitic crystal cell of the alloy.The formation of strong covalent bond between C and me- tallic elements can vigorously retard the γ/α' transformation.

HYDROGEN IN Pd-In ALLOYS

The equilibrium p-c-T data were determined by a microbalance in a vacuum system at hydrogen pressures up to 3.5 MPa on four Pd-In alloys between 3.64 and 14.53 at. % In as well as on Pure Pd. The results are similar to those obtained on the analogous alloys Pd-Ag and Pd-Sn and are interpreted in the same manner. In has two opposing effects upon the solubility of H in the Pd alloys, i.e., increase of the Fermi energy upon the donation of valence electrons and a lattice dilatation. At valence electron concentrations below 0.5, the lattice dilatation predominates and the H solubility is increased with addition of In. At valence electron concentrations above 0.5, the influence of the elevated Fermi energy predominates and the H solubility is lowered by addition of In. The molar enthalpy of Pd hydriding at infinite dilution is strongly increased with increasing In content, but the molar entropy is not nearly as much affected by the Presence of In. The excess chemical potential of hydrogen at small hydrogen concentrations and at a given temperature increases with an increase of In content. The apparent H-H attractive interaction energy, W H-H, is decreased by the presence of In. The trend is also similar to that found for the Pd-Ag-H and Pd-Sn-H system.

THE CALCULATION OF THE COHESIVE ENERGY OFГPHASE IN THE TRANSITIONAL LAYER FE ZN OF HEAT GALVANIZED SHEET USED IN CARS

hethesisanalysesthevalenceelectronstructuresof phase Γin Fe Zn transitionallayerof heat galvanized sheet used in cars by applying the Empirical Electron Theory of Solids andMolecules, and calculatesthebond energy ofthe major bondsand cohesiveenergy ofcrystals,from which we draw theconclusion:sincecrystal has alargercohesiveenergy, it has higherhardness, butsinceitsbondenergyisratherlow ,itiseasytobreak under pressurefrom out side, and thecrackiseasytocome up andspreadin phase Γ.

Delocalizedπ_(3)^(6) Bond in OX_(2) (X=Halogen) Molecules

OX_(2)(X=halogen)molecules was studied theoretically.Calculation results show that delocalizedπ_(3)^(6) bonds exist in their electronic structures and O atoms adopt the sp^(2) type of hybridization,which violates the prediction of the valence shell electron pair repulsion theory of sp^(3) type.Delocalization stabilization energy is proposed to measure the contribution of delocalizedπ_(3)^(6) bond to energy decrease and proves to bring extra-stability to the molecule.These phenomena can be summarized as a kind of coordinating effect.