The Application of SCC-DV-X_a Computational Method of Quantum Chemistry in Cement Chemistry

It has been explored why quantum chemistry is applied to the research field of cement chemistry. The fundamental theory of SCC-DV-Xα computational method of quantum chemistry is synopsized. The results obtained by computational quantum chemistry method in recent years of valence-bond structures and hydration activity of some cement clinker minerals, mechanical strength and stabilization, of some hydrates are summarized and evaluated. Finally the prospects of the future application of quantum chemistry to cement chemistry are depicted.

CaO-Al_2O_3系统铝酸钙矿物水化活性差异的SCC-DV-X_α方法研究

建立了ＣａＯ－Ａｌ２Ｏ３系统Ｃ３Ａ，Ｃ１２Ａ７，ＣＡ，ＣＡ２和ＣＡ６５种铝酸钙化合物的计算模型并分别对它们进行了量子化学的电荷自洽离散变分Ｘα法（ＳＣＣ－ＤＶ－Ｘα）计算．计算结果表明：５种矿物的Ｃａ—Ｏ共价键级大小呈Ｃ３Ａ＜Ｃ１２Ａ７＜ＣＡ＜ＣＡ２＜ＣＡ６排列，最低空分子轨道（ＬＵＭＯ）与最高占据分子轨道（ＨＯＭＯ）能级之差也基本按上述顺序呈递增趋势，可以认为这是以上５种矿物水化活性依序降低的主要原因．

量子化学SCC-DV-X_α计算方法在水泥化学研究中的应用

探讨了量子化学在水泥化学领域应用研究的基本思想，对近几年来应用量子化学ＳＣＣＤＶＸα计算方法研究一些水泥熟料矿物价键结构与水化活性、水化产物相的力学强度和稳定性等问题所得到的结果进行了综述与评价。

Solvothermal Syntheses, Crystal Structures, Thermal Stability and Quantum Chemistry of Dinuclear Trialkyltin Complexes Constructed by Camphoric Acid

Two dinuclear organotin complexes C8H14（CO2SnCy3）2（1）（Cy = cyclohexyl group） and C8H14[CO2Sn（CH2CMe2Ph）3]2（2） were synthesized by the reactions of camphoric acid with tricyclohexyltin hydroxide and bis[tri（2-methyl-2-phenyl）propyltin] oxide under solvothermal conditions, and these complexes were characterized by infrared spectra, elemental analyses, and H NMR spectra. The crystal of 1 belongs to the monoclinic system, space group P21/c with a = 1.83478（19）, b = 1.52707（18）, c = 1.9849（2） nm, β = 122.515（7）°, Z = 4, V = 4.6896（9） nm^3, Dc = 1.324 g/cm^3, μ（MoKα） = 1.103 mm^-1, F（000） = 1952, R = 0.0697 and wR = 0.2040. In addition, thermal stability and quantum chemical calculation of 1 were also studied.

Recent progress on discovery and properties prediction of energy materials:Simple machine learning meets complex quantum chemistry

In nature,the properties of matter are ultimately governed by the electronic structures.Quantum chemistry(QC)at electronic level matches well with a few simple physical assumptions in solving simple problems.To date,machine learning(ML)algorithm has been migrated to this field to simplify calculations and improve fidelity.This review introduces the basic information on universal electron structures of emerging energy materials and ML algorithms involved in the prediction of material properties.Then,the structure-property relationships based on ML algorithm and QC theory are reviewed.Especially,the summary of recently reported applications on classifying crystal structure,modeling electronic structure,optimizing experimental method,and predicting performance is provided.Last,an outlook on ML assisted QC calculation towards identifying emerging energy materials is also presented.

Quantum Chemistry Calculations on the Interaction Between Kaolinite and Gold

The density,function and discrete variation method (DFT - DVM) is used to study the interaction between kaolinite and gold. The correlation among the structure, chemical bond and stability is discussed. Several models are selected without gold and with gold in different directions and sites. The results show that the models with gold on the edge of kaolinite basal layer are more stable than those with gold above or under the layer, the models with gold near to [AlO2 (OH)(4)] octahedra are more stable than those with gold near to the vacancy without aluminium. The interaction between gold and the surface ions of kaolinite is strong enough to form the surface complexes.

Quantum confinement and surface chemistry of 0.8–1.6 nm hydrosilylated silicon nanocrystals

In the framework of density functional theory （DFT）, we have studied the electronic properties of alkene/alkyne- hydrosilylated silicon nanocrystals （Si NCs） in the size range from 0.8 nm to 1.6 nm. Among the alkenes with all kinds of functional groups considered in this work, only those containing -NH2 and -C4H3S lead to significant hydrosilylation- induced changes in the gap between the highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO） of an Si NC at the ground state. The quantum confinement effect is dominant for all of the alkene- hydrosilylated Si NCs at the ground state. At the excited state, the prevailing effect of surface chemistry only occurs at the smallest （0.8 nm） Si NCs hydrosilylated with alkenes containing -NH2 and -C4H3S. Although the alkyne hydrosilylation gives rise to a more significant surface chemistry effect than alkene hydrosilylation, the quantum confinement effect remains dominant for alkyne-hydrosilylated Si NCs at the ground state. However, at the excited state, the effect of surface chemistry induced by the hydrosilylation with conjugated alkynes is strong enough to prevail over that of quantum confinement.

A Benzimidazole-pyridine-2,3-dicarboxylic Acid Bridged Zinc(Ⅱ)Coordination Complex–crystal Structure,Quantum Chemistry and Luminescence

The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and luminescence. Chemical formula： C14 H10 N3 O5 Zn1.5. It crystallizes in the monoclinic system, space group P21/c with a = 12.303（4）, b = 12.052（4）, c = 10.212（3） ？, β = 104.147（4）, V = 1468.3（8） ？3, Z = 4, Mr = 398.30, Dc = 1.802 g/cm3, F（000） = 800, μ = 2.501 mm-1 and S = 1.000. The 2-D network architecture of 1 is constructed from benzimidazole, zinc and pyridine-2,3-dicarboxylic acid. The quantum-chemical calculations have been performed on ‘molecular fragments’ extracted from the crystal structure using the B3 LYP method in Gaussian 09. The luminescence spectrum shows that complex 1 emits blue luminescence.

A Quantum Chemistry Study on Structural Properties of Petroleum Resin

The geometries of resins with single-layer （SG）, double-layer （DG） and triple-layer （TG） were calculated with the quantum chemistry method. The geometries and net charges of atoms were obtained. The calculated average distances between layers were 0.5348 nm and 0.5051 nm and the action energies were -9.6355 kJ/mol and -32.2803 kJ/mol for resins DG and TG, respectively. Higher electronegative polar atoms can easily form hydrogen bonds with hydrogen atoms of other resin molecules, resulting in resin aggregates. The minimum cross-sectional diameters of resin molecules are too large to enter the pores of zeolite, so they are likely to crack on the surface of zeolite.

QUANTUM CHEMISTRY STUDIES ON THE STRENGTH PERFORMANCE OF ETTRINGITE

Ettringite is a main hydrate of cement, and the Sr-bearing ettringite is a main hydrate of Sr-bearing calcium suplhoaluminate. In this paper the two hydrates are studied by a quantum chemistry method, the self-consistent-field discrete variation X(alpha) method (SCC-DV-X(alpha)) The results show: their bond order of Al and covalent bond order of Al-O bond are alike; that the bond order of Sr and the covalent bond order of Sr-O in Sr-bearing ettringite are higher than these of ettringite is the main reason, that the strength of Sr-bearing ettringite is higher than that of ettringite.

Formation Mechanism of Biomass Aromatic Hydrocarbon Tar on Quantum Chemistry

The formation process of aromatic hydrocarbon tar during the pyrolysis process of biomass components of cel-lulose and lignin was carried out by quantum chemical calculation based on density functional theory method B3LYP/6-31G++(d,p).5 Hydroxymethylfurfural was chosen as the model compound of cellulose and hemicel-lulose,and syringa ldehyde was chosen as the model compound of lignin.The calculation results show that the formation process of cellulose monocyclic aromatic hydrocarbon tar is the conversion process of benzene ring from furan ring,and the highest reaction energy barrier appears in the process of decarbonylation,which is 370.8 kJ/mol.The formation of lignin monocyclic aromatic hydrocarbon tar is mainly the process of side chains removal and the formation of phenol,The highest reaction energy barrier appears in the process of decarbonyla-tion,which is 374.9 kJ/mol.The reaction mechanism of phenanthrene formation from naphthalene was selected as the formation of cellulose and lignin polycydic aromatic hydrocarbon tar.The calculation results show that he total barrier of the pathway that naphthalene dehydrogenates to form naphthalene free radicals and then reacts with ethylene twice by addition action,finally occurs cydization reactions and isomerizes to produce phenan-threne is lowest,that is 38.6 kJ/mol.So it is proved that the evolution of tar is the process of deoxygenation and cyclization with the increase of the temperature from a theoretical point of view.

STURCTURAL CHARACTERISTICS AND QUANTUM CHEMISTRY CALCULATION OF AI-DOPED BORON CARBIDES

Structural characteristics, chemical bonds and thermoelectric properties of Al-doped boron carbides are studied through calculations of various structural unit models by using a self-consistent-field discrete variation X. method. The calculations show that Al atom doped in boron carbide is in preference to substituting B or C atoms on the end of boron carbide chain, and then may occupy interstitial sites, but it is difficult for Al to substitute B or C atom in the centers of the chain or in the icosahedra. A representative structural unit containing an Al atom is [C - B -Al]-[B11C]-,while the structural unit without Al is [C-B-B(C)]- - [B11C]C+, and the coexistence of these two different structural units makes the electrical conductivity increased. As the covalent bond of Al-B or Al-C is weaker than that of B-B or B-C, the thermal conductivity decreases when Al is added into boron carbides. With the electrical conductivity increasing and the thermal conductivity decreases, Al doping has significant effect on thermoelectric properties of baron carbides.

Quantum Chemistry Calculation of Quercetin-silver Complex

Three possible molecular structures of quercetin-silver complexes obtained from the reaction of quercetin and Ag^＋ in equivalent molar ratio were designed and optimized by using Gaussian 98 program at the B3LYP/LanL2DZ basis set. Through theoretical analysis, one of the three designed structures is discovered to have the most stable coordination position. Then its geometry structure, natural bond orbital analyses, vibrational frequency and biological activity were performed. The results show that it has good stability and relatively stronger antioxidative activity because it is favorably attacked by O2^-. Therefore theoretical foundation is provided for the development of new quercetin metal complexes with higher activity antioxidants.

Surface chemistry of MXene quantum dots:Virus mechanism-inspired mini-lab for catalysis

Scientific research is currently more interdisciplinary.Researchers have parsed the surface structure of virus,constructed the interaction model of virus-receptors,offering the clues for studying efficient targeted drugs.Likewise,catalysis is also highly relevant to modern human life.Exploring the surface structure and physicochemical properties of catalysts is of great significance for the design of efficient catalysts.Great progresses have been made for endowing specific physicochemical properties of catalysts through controlling the size of materials and coordination chemistry of active sites,particularly at nanometer scale since Sir John Meurig Thomas and Tao Zhang’s early ground-breaking contribution,with casting on a very surface issue.Herein,functional regulation renders the emerging MXene quantum dots(MQDs)excel in contrast to the typical carbon-based quantum dots.In fact,similar to the interaction of virus-receptors model,the surface functional groups decorated MQDs provide a mini-lab to afford a variety of adjustments,involved with the type modification and electronic structure tuning of groups as well as their arrangement,together with the interaction between the groups and active materials/support,ultimately for packaging or designing high-activity catalysts.

Quantum Chemistry Prediction of Molecular Lipophilicity Using Semi-Empirical AM1 and <i>Ab Initio</i>HF/6-311++G Levels

Reliable prediction of lipophilicity in organic compounds involves molecular descriptors determination. In this work, the lipophilicity of a set of twenty-three molecules has been determined using up to eleven quantum various descriptors calculated by means of quantum chemistry methods. According to Quantitative Structure Property Relationship (QSPR) methods, a first set of fourteen molecules was used as training set whereas a second set of nine molecules was used as test set. Calculations made at AM1 and HF/6-311++G theories levels have led to establish a QSPR relation able to predict molecular lipophilicity with over 95% confidence.

Quantum Chemistry Based Computational Study on the Conformational Population of a Neodymium Neodecanoate Complex

The title complex is widely used as an efficient key component of Ziegler-Natta catalyst for stereospecific polymerization of dienes to produce synthetic rubbers. However, the quantitative structure-activity relationship（QSAR） of this kind of complexes is still not clear mainly due to the difficulties to obtain their geometric molecular structures through laboratory experiments. An alternative solution is the quantum chemistry calculation in which the comformational population shall be determined. In this study, ten conformers of the title complex were obtained with the function of molecular dynamics conformational search in Gabedit 2.4.8, and their geometry optimization and thermodynamics calculation were made with a Sparkle/PM7 approach in MOPAC 2012. Their Gibbs free energies at 1 atm. and 298.15 K were calculated. Population of the conformers was further calculated out according to the theory of Boltzmann distribution, indicating that one of the ten conformers has a dominant population of 77.13%.

Neural Network Based on Quantum Chemistry for Predicting Melting Point of Organic Compounds

The melting points of organic compounds were estimated using a combined method that includes a backpropagation neural network and quantitative structure property relationship （QSPR） parameters in quantum chemistry. Eleven descriptors that reflect the intermolecular forces and molecular symmetry were used as input variables. QSPR parameters were calculated using molecular modeling and PM3 semi-empirical molecular orbital theories. A total of 260 compounds were used to train the network, which was developed using MatLab. Then, the melting points of 73 other compounds were predicted and results were compared to experimental data from the literature. The study shows that the chosen artificial neural network and the quantitative structure property relationships method present an excellent alternative for the estimation of the melting point of an organic compound, with average absolute deviation of 5%.

Reaction Activity of Kao linite Surfaces:Quantum Chemistry Calculations

The anion kaolinite surface interactions and AuS - adsorption onto the surfaces of kaolinite were studied using the self consistent field discrete variation (SCF-X α-DV) method.Electronic structure and energies of the system of anion AuS - adsorbed on an atomic cluster of kaolinite were calculated.The results show that the systems with lower total energy are those AuS - adsorbed on the edge surfaces,which indicates that the systems of adsorption of AuS - on the edges are more stable relative to those adsorbed on the basal plane.On the other hand,bond order data suggest that significant shifting of atomic charge and the overlapping of electronic cloud between Au (Ⅰ) of the AuS - and the surface ions of kaolinite would take place in the systems with AuS - being adsorbed on the edges,especially at the site near Al octahedra.Therefore,it can be concluded that edge sites will dominate the complexation reactions of the surfaces of kaolinite,with negligible contributions from other functional groups on the basal plane,which are dominated by either siloxane sites in silica layers or aluminol sites in gibbsite layers.

Quantum Chemistry Studies on the Difference of Structures and Electronic Properties of Polyacene,Polypyridinopyridine and Paracyanogen

Polyacene (PAS), polypyridinopyridine (PPyPy) obtained by substitution of -N = for -CH = in PAS, and paracyanogen (Pc) molecules have been studied using quantum chemistry MNDO, 1D tight-binding CNDO/2-CD methods. The analyses of the energy band structures indicate that the substitution of N atoms changes the molecular structures and increases the activity points of electrophilic or nucleophilic doping, but intrinsical conductivity is not improved.

The Quantum Chemistry Calculation and Thermoelectricsof Bi-Sb-Te Series

The density junction theory and discrete variation method ( DFT - DVM) was used to study correlation between composition, structure, chemical bond, and property of thermoelectrics of Bi-Sb-Te series. 8 models of Bi20-xSbxTe32(x = 0,2,6,8,12,14,18 and 20) were calculated. The results show that there is less difference in the ionic bonds between Te( I)-Bi(Sb) and Te(Ⅱ)-Bi(Sb) , but the covalent bond of Te(Ⅰ)-Bi( Sb ) is stronger than that of Te(Ⅱ)-Bi( Sb ) . The interaction between Te(Ⅰ) and Te(Ⅰ) in different layers is the weakest and the interaction should be Van Der Wools power. The charge of Sb is lower than that of Bi, and the ionic bond of Te-Sb is weaker than that of Te-Bi. The covalent bond of Te-Sb is also weaker than that of Te-Bi. Therefore, the thermoelectric property may be imfiroved by adjusting the electrical conductivity and thermal conductivity through changing the composition in the compounds of Bi-Sb-Te. The calculated results are consistent with the experiments.