Estimating heat capacities of liquid organic compounds based on elements and chemical bonds contribution

Molecular property depends on the property, the number of the elements, and the interaction between elements(such as chemical bonds). Based on the above-mentioned idea, two methods to estimate the isobaric heat capacity of liquids organic compounds were developed. Ten elements groups and 32 chemical bond groups were defined by considering the structure of organic compounds. The group contribution values and correlation parameters were regressed by the ridge regression method with the experiment data of 1137 compounds. The heat capacity can be calculated by summating the contributions of the elements and chemical bond groups. The two methods were compared with existing group contribution methods, such as Chickos, Zabransky-Ruzicka, and Zdenka Kolska. The results show that those new estimation methods' overall average relative deviations were 5.81% and 5.71%, which were lower than the other three methods. Those methods were more straightforward in compound splitting.Those new methods can be used to estimate the liquid heat capacity of silicon-containing compounds,which the other three methods cannot estimate. The new methods are more accessible, broader, and more accurate. Therefore, this research has important scientific significance and vast application prospects.

Electronic Structures and Chemical Bonds of Cobaltite and Ni-Doped

The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co2 O6 and Ni-doped was studied by density function theory and discrete variation method（DFT-DVM）. The results indicate that the highest valence band（ HVB ）attd the lowest conduction band（ LCB ） are mainly attribuled to Co3d, Ni3d and O2p atomic orbitals. The property of a semiconductor is shown from the gap between HVB and LCB. The gap of Ni-doped one is less than that of Ca3 Co2 O6. The non-metal bond or ceramic characteristic of Ni-doped one is weaker than that of Ca3 Co2 O6, but the metal characteristics of Ni-doped one are stronger than those of Ca3 Co2 O6. The thermoelectric property should be improved by adding Ni element into the system of Ca3 Co2 O6 .

CCSD(T) study on the structures and chemical bonds of AnO molecules (An = Bk–Lr)

The molecular geometries and dissociation energies of AnO (An = Bk–Lr) molecules were first obtained at thecoupled-cluster single-, double-, and perturbative triple-excitations [CCSD(T)] level of theory. Four hybrid functionals,B3LYP, M06-2X, TPSSh, and PBE0, were also employed in the calculations for the sake of comparison. In comparison ofthe CCSD(T) results, B3LYP, TPSSh, and PBE0 functionals can obtain more appropriate results than M06-2X and MP2.The analyses on molecular orbitals show that the 7s, 6d, and 5f atomic orbitals of actinide (An) atoms participate in thebonding of An–O bonds. The partial covalent nature between An and O atoms is revealed by QTAIM analyses.

Design method of extractant for liquideliquid extraction based on elements and chemical bonds

In the petrochemical industry process,the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate.Liquideliquid extraction is a common and effective separation method,and selecting an extraction agent is the key to extraction technology research.In this paper,a design method of extractants based on elements and chemical bonds was proposed.A knowledge-based molecular design method was adopted to pre-select elements and chemical bond groups.The molecules were automatically synthesized according to specific combination rules to avoid the problem of“combination explosion”of molecules.The target properties of the extractant were set,and the extractant meeting the requirements was selected by predicting the correlation physical properties of the generated molecules.Based on the separation performance of the extractant in liquideliquid extraction and the relative importance of each index,the fuzzy comprehensive evaluation membership function was established,the analytic hierarchy process determined the mass ratio of each index,and the consistency test results were passed.The results of case study based on quantum chemical analysis demonstrated that effective determination of extractants for the analysis of benzeneecyclohexane systems.The results unanimously prove that the method has important theoretical significance and application value.

Reversible grafting of antibiotics onto contact lens mediated by labile chemical bonds for smart prevention and treatment of corneal bacterial infections

Eye trauma, decreased immunity, and contact lens wear often cause serious bacterial infections and irreversible corneal damage. To realize the responsive release of antibiotics such as gentamicin sulfate(GS), a novel antibacterial contact lens was constructed through self-assembly of antibiotics loaded ADAGS/PEI(polyethyleneimine) multilayer films on the surface. Both in vitro and in vivo antibacterial tests demonstrated high efficient and fast antibacterial property based on the smart responsive to bacterial infections and reversible drug loading and release.

Chemical Bonds and Dielectric Constants of REM（RE＝Rare Earth，M＝N，P，As，Sb）Crystals

By using Pillips and van Vechten theory, the chemical bond parameters and dielectric constants of REM (RE=rare earth,M=N,P,As,Sb) crystals were calculated.The values calculated of dielectric constants agree with the experimental values.

Chemical bonding of perovskite LaFeO_(3) with Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2) to moderate anion redox for achieving high cycling stability

Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.

Geometries and electronic structures of Zr_(n)Cu(n=2–12) clusters: A joint machine-learning potential density functional theory investigation

Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.

Systematic Method for Constructing Lewis Representations

The systematic method for constructing Lewis representations is a method for representing chemical bonds between atoms in a molecule. It uses symbols to represent the valence electrons of the atoms involved in the bond. Using a number of rules in a defined order, it is often better suited to complicated cases than the Lewis representation of atoms. This method allows us to determine the formal charge and oxidation number of each atom in the edifice more efficiently than other methods.

Recent progress on confinement of polysulfides through physical andchemical methods

With high theoretical energy density and the natural abundance of S, lithium-sulfur （Li-S） batteries areconsidered to be the promising next generation high-energy rechargeable energy storage devices. How-ever, issues including electronical insulation of S, the lithium polysulfides （LiPSs） dissolution and the shortcycle lifespan have prevented Li-S batteries from being practical applied. Feasible settlements of confiningLiPSs to reduce the loss of active substances and improve the cycle stability include wrapping sulfur withcompact layers, designing matrix with porous or hollow structures, adding adsorbents owning stronginteraction with sulfur and inserting polysulfide barriers between cathodes and separators. This reviewcategorizes them into physical and chemical confinements according to the influencing mechanism. Withfurther discussion of their merits and flaws, synergy of the physical and chemical confinement is believedto be the feasible avenue that can guide Li-S batteries to the practical application.

Solution-based Chemical Strategies to Purposely Control the Microstructure of Functional Materials

Micro/nanostructured crystals with controlled architectures are desirable for many applications in optics, electronics, biology, medicine, and energy conversions. Low-temperature, aqueous chemical routes have been widely investigated for the synthesis of particles, and arrays of oriented nanorods and nanotubes. In this paper, based on the ideal crystal shapes predicted by the chemical bonding theory, we have developed some potential chemical strategies to tune the microstructure of functional materials, ZnS and Nb205 nanotube arrays, MgO wiskers and nestlike spheres, and cubic phase Cu2O microcrystals were synthesized here to elucidate these strategies. We describe their controlled crystallization processes and illustrate the detailed key factors controlling their growth by examining various reaction parameters. Current results demonstrate that our designed chemical strategies for tuning microstructure of functional materials are applicable to several technologically important materials, and therefore may be used as a versatile and effective route to the controllable synthesis of other inorganic functional materials.

Electronic Structure and Chemical Bond of Titanium Diboride

Titanium diboride was calculated by the density function and discrete variational (DFT-DVM) method to study the relation between structure and properties.Titanium and its first-nearest boron atoms form a strong covalent bond,so TiB 2 has high melting point,hardness and chemical stability.Titanium atom releases two electrons to form Ti 2+ ions,and a boron atom gets one electron to come into B- ion.B- takes the sp2 hybrid and forms σ bonds to link other boron atoms in the same layer.The other one 2p z orbital of every B- ion in the same layer interacts each other to form the π molecular orbital,so TiB 2 has fine electrical property.The calculated density of state is close to the result of XPS experiment of TiB 2.Mainly Ti3d and B2p atomic orbitals contribute the total DOS near the Fermi level.

Electronic Structure and Chemical Bond of Ti_3SiC_2 and Adding Al Element

The relation among electronic structure, chemical bond and property of Ti3SiC2 and Al-doped was studied by density function and discrete variation （ DFT- DVM） method. When Al element is added into Ti3 SiC2 , there is a less difference of ionic bond, which does not play a leading role to influent the properties. After adding Al, the covalent bond of Al and the near Ti becomes somewhat weaker, but the covalent bond of Al and the Si in the same layer is obviously stronger than that of Si and Si before adding. Therefore, in preparation of Ti3 SiC2 , adding a proper quantity of Al can promote the formation of Ti3 SiC2 . The density of stnte shows that there is a mixed conductor character in both of Ti3 SiC2 and adding Al element. Ti3 SiC2 is with more tendencies to form a semiconductor. The total density of state near Fermi lever after adding Al is larger than that before adding, so the electric conductivity may increase after adding Al.

Effect of Microsilica on Chemical Bond of Calcium Aluminate Cement Bonded Corundum Castable at Low and Intermediate Temperatures

Calcium aluminate cement bonded corundum castable specimens were prepared using brown fused corundum （8 - 5, 5 - 3, 3 - 1 mm ） , white fused corundum （ ≤ 1, ≤0. 045 mm）, micro-sized α-Al2O3 and microsilica as starting materials. This work focused on investigating the relationship between the bond change in the castable matrix and the strength of the castable with 5 mass% microsilica or without microsilica after heat treatment at 110, 800 and 1 000 ℃, respectively. Chemical bond changes between the microsilica and hy- drates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃ were investigated by XPS and FTIR. The results show that Si-O-Al bonds form be- tween the microsilica and hydrates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃. Therefore, the increased strength of castable specimens is attributed to the formation of Si-O-Al bonds from 110 ℃ to 800 ℃.

Investigation of Chemical Bond Properties and Mssbauer Spectroscopy in YBa_2Cu_3O_7

Chemical bond properties of YBa 2Cu 3O 7 were studied by using the average ba nd-gap model. The calculated results show that the covalency of Cu(1)-O bond i s 0.406, and one of Cu(2)-O is 0.276. Mssbauer isomer shifts of 57Fe in Y-123 were calculated by the chemical surrounding factor h v defined b y covalency and electronic polarizability. The charge-state and site of Fe were determined. The relation between the coupling constant of electron-phonon inte raction and covalency is employed to explain that the Cu(2)-O plane is more im portant than the Cu(1)-O chain on the superconductivity in the Y-123 compound s.

Chemical bond properties and M(?)ssbauer spectroscopy in (La_(1-x)M_x)_2CuO_4(M=Ba,Sr)

By using the average band-gap model, the chemical bond properties of(La_(1-x)M_x)_2CuO_4(M=Ba, Sr) were calculated . The calculated covalencies for Cu-O and La-O bondin the compounds are 0.3 and 0.03 respectively. Mossbauer isomer shifts of ^(57)Fe doped inLa_2CuO_4 and ^(119)Sn doped in La_2CuO_4 were calculated by using the chemical surrounding factordefined by covalency and electronic polarizability. Four valence state tin and three valence ironsites were identified in ^(57)Fe and ^(119)Sn

ON STRUCTURES,PROPERTIES AND CHEMICAL BOND OF Te-Se-I GLASS AND OF ADDING As,Ge ELEMENTS ONE

Te-Se glass and adding As,Ge elements to it are studied with Selt-Consistent-Field Discrete Variatioal X(a) (SEF-DV-X(a)), one of the molecule orbital calculating methods in quantum chemistry. The chemical bonding is used to discuss the relations between structures and properties with the varations of compositions of the glasses. The calculated results show that the strength of covalent and ionic bonds are both in the order of Ge-Se > As-Se > Te-Se, which is consistent with the experimental result of the glass-transition temperature (T-g) of the corresponding grasses. The Te-I bond in which I atom is one-coordinate is stronger than that in which I atom is two-coordinate, As-I and As-As bonds are both stronger than the two types of Te-I bonds. The waek Te-I bonds have been replaced by the stronger As-I and As-As bonds, which is just the reason why As addition in TeX glasses can obviously improve the thermal and chemical properties.

Chemical Reaction Between Polyvinyl Alcohol and Titanate Coupling Agent with X-Ray Photoelectron Spectroscopy

The chemical reaction between polyvinyl alcohol (PVA) and tri(dioctylpyrophosphoryloxy) isopropyl titanate (NDZ-201) was studied using X-ray photoelectron spectroscopy (XPS).The results show that some C-OH functional groups of PVA react with the titanate coupling agent to form C PVA-O-Ti-O-C PVA bond.The cross-linking of the PVA chains occurs through the formation of C PVA-O-Ti-O-C PVA bonds and produces a three dimensional hydrophobic polymer network.Accordingly,the mechanism is proposed that the titanate coupling agent improves the moisture sensitivity of high alumina cement/polyvinyl alcohol (HAC/PVA) based macro defect free (MDF) composite material.

Electronic Structure and Chemical Bonding of a Tetranuclear Neodymium Complex Nd_4O(OR)_4(NR'_2)_6

The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central μ_4-O atom and the four Nd atoms.The results of calculation show that the μ_4-O atom uses its sp^3 valence orbitals to contribute four O-Nd bonding MOs with character of multicenter bond apparent- ly.The Mulliken population analysis shows that the overlap population between Nd atoms is almost equal to zero,therefore there is no direct metal-metal bond between Nd atoms.The coordination number of Nd in the complex is discussed briefly.

Non-standard tests for process control in chemically bonded sands

Chemically bonded sand cores and molds are more commonly referred to as precision sand systems in the high production automotive powertrain sector. Their behavior in contact with molten metal can lead to casting defects. Consequently, the interaction is of great interest and an important part of metal casting technology. The American Foundry Society(AFS) sand testing is based on physical, mechanical, thermal and chemical properties of the sand system. Foundry engineers have long known that certain AFS sand tests provide limited information regarding control of molding and casting quality. The inadequacy is due to the fact that sand casting processes are inherently thermo-mechanical, thermo-chemical and thermo-physical. Non-standard foundry sand testing has proven useful for laboratory measurement of these characteristics in foundry sand using a disc-shaped specimen. Similarly, the equivalent disc-shaped specimens are used for casting trials. In order to accomplish near-net-shape casting with minimal defects, it is necessary to understand both the properties of the sand system, as well as the interface of molten metal when different binders, additives and/or refractory coatings are used. The methodology for the following non-standard chemically bonded sand tests is described:(1) disc transverse;(2) impact;(3) modified permeability;(4) abrasion;(5) thermal distortion;(6) quick loss on ignition. The data related to the non-standard sand tests were analyzed and interpreted. The test results indicate that there is relatively lower test-to-test variability with the disc-shaped specimens. The non-standard tests were able to discriminate between the chemically bonded polyurethane cold box sand specimens. Further studies should be conducted on various other sand and binder systems as well as on different specimen thicknesses.