This study presents a predictive model for condensed-phase heats of formation of metal-containing energetic complexes(MCECs)and energetic metal-organic frameworks(EMOFs),leveraging a dataset of 148 compounds.Using ele...This study presents a predictive model for condensed-phase heats of formation of metal-containing energetic complexes(MCECs)and energetic metal-organic frameworks(EMOFs),leveraging a dataset of 148 compounds.Using elemental composition,triazole rings,and metal presence,the model achieves high accuracy(R^(2)>0.94,mean absolute error(MAE)≈390 kJ/mol)for screening high-energy materials.It outperforms prior methods,particularly for polycyclic systems,offering a practical tool for safer design and risk assessment in defense and industrial applications.展开更多
As mining activities expand deeper,deep high-temperature formations seriously threaten the future safe exploitation,while deep geothermal energy has great potential for development.Combining the formation cooling and ...As mining activities expand deeper,deep high-temperature formations seriously threaten the future safe exploitation,while deep geothermal energy has great potential for development.Combining the formation cooling and geothermal mining in mines to establish a thermos-hydraulic coupling numerical model for fractured formation.The study investigates the formation heat transfer behaviour,heat recovery performance and thermal economic benefits influenced during the life cycle.The results show that the accumulation of cold energy during the cold storage phase induces a decline in formation temperature.The heat recovery phase is determined by the extent of the initial cold domain,which contracts inward from the edge and decelerates the heat recovery rate gradually.With groundwater velocity increases,the thermal regulation efficiency gradually increases,the production temperature decreases,while the effective radius and thermal power increase first and then decrease.The injected volume and temperature significantly affect,with higher injection temperatures slowing thermal recovery,and the thermal regulation efficiency is more sensitive to changes in formation permeability and thermal conductivity.The heat extraction performance is positively correlated with all factors.The levelized cost of electricity is estimated at 0.1203$/(kW·h)during the cold storage.During the heat recovery,annual profit is primarily driven by cooling benefits.展开更多
A semi-empirical calculation of the heat of formation was applied to ternary system: La-Fe-Al,Fe-Ni-V and Cu-Pd-Si.The calculated values were compared with the experimental ones and the coincidence was satisfactory.Th...A semi-empirical calculation of the heat of formation was applied to ternary system: La-Fe-Al,Fe-Ni-V and Cu-Pd-Si.The calculated values were compared with the experimental ones and the coincidence was satisfactory.This method is helpful to predict the stabilities of ternary compounds and solid solubility.展开更多
The ionization energies （IEs） of cyclopropenylidene （c-C3H2）, propargylene （HCCCH） and propadienylidene （H2CCC） have been computed using the CCSD（T）/CBS method, which involves the approxixnation to the compl...The ionization energies （IEs） of cyclopropenylidene （c-C3H2）, propargylene （HCCCH） and propadienylidene （H2CCC） have been computed using the CCSD（T）/CBS method, which involves the approxixnation to the complete basis set （CBS） limit at the coupled cluster level with single and double excitations plus quasi-perturbative triple excitation effect （CCSD（T））. The zero-point vibrational energy correction, the core-valence electronic correction, the scalar relativistic effect and the high level correction beyond the CCSD（T） excitations have also been made in these calculations. The CCSD（T）/CBS values for the IN（c-C3H2） and IE（HCCCH） of 9.164, 8.987 eV are in good agreement with the experimental values of （9.15±0.03） and （8.96±0.04） eV. The CCSD（T）/CBS calculations yield the IE values of 10.477 and 10.388 eV for the ionization transitions H2CCC→H2CCC^＋ （^2A1, C2v） and H2CCC→H2CCC＋ （^2A＇, Cs）, respectively. On the basis of the Franek-Condon factor consideration, the IE of （10.43±0.02） eV determined in the previous single-photon ionization experiment most likely corresponds to the ionization threshold for the H2CCC→H2CCC^＋（^2A1, C2v） transition. Although the precision of the experimental IN measurements fpr c-C3H2, HCCCH, and H2CCC is insufficient to pin down the accuracy of the theoretical calculations to better than ±30 meV, the excellent agreement between the experimental and theoretical IE values observed in the present study indicates that the CCSD（T）/CBS calculations together with high-order correlation corrections are capable of yielding reliable IE predictions for simple hydrocarbon carbenes and bi-radicals. We have also reported the heats of formation at 0 K （△H^of0） and 298 K （△H^of298）for c-C3H2/c-C3H2^＋, HCCCH/HCCCH^＋, and H2CCC/H2CCC^＋, The available experimental △H^of0 and △H^of298 values for c-C3H2/c C3H2^＋, HCCCH/HCCCH^＋ are found to be in good accord with the CCSD（T）/CBS predictions after taking into account the experimental uncertainties.展开更多
In this paper, the nonlinear stationary waves forced by topography and diabatic heating are investigated. It is pointed out that (1) the nonlinear interaction of different stationary waves forced only by topography mi...In this paper, the nonlinear stationary waves forced by topography and diabatic heating are investigated. It is pointed out that (1) the nonlinear interaction of different stationary waves forced only by topography might form dipole blocking in the atmosphere, this might explain the dipole blocking appeared in the Pacific and Atlantic regions; (2) the dipole blocking could not be caused by the nonlinear interaction of the different stationary waves forced by the diabatic heating alone; (3) the nonlinear interaction of the diffferent stationary waves forced by both topography and diabatic heating could initiate dipole blocking in the atmosphere. In winter, the dipole blocking mainly occurs in the west regions of the Pacific and the Atlantic, and the heat source over the western part of the two oceans is advantageous to the formation of dipole blocking in the west of two oceans. However, in summer, the dipole blocking could be formed in the east part of the two oceans, and the heat source over the eastern part of two continents is favourable for the formation of dipole blocking in the east regions of two oceans.展开更多
The formation process and composition of the acrylonitrile/urea inclusion compounds （AN/UIC） with different aging times and AN/urea molar feed ratios are studied by differential scanning calorimetry （DSC） and X-ra...The formation process and composition of the acrylonitrile/urea inclusion compounds （AN/UIC） with different aging times and AN/urea molar feed ratios are studied by differential scanning calorimetry （DSC） and X-ray diffraction （XRD）. It is suggested that DSC can determine the vip/host ratio and the heat of decomposition. Meanwhile, the vip/host ratio and heat of decomposition are obtained, which are 1.17 and 5361.53 J/mol, respec- tively. It is suggested AN molecules included in urea canal lattice may be packed flat against each other. It is found that the formation of AN/UIC depends on the aging time. XRD results reveal that once AN molecules enter urea lattice, AN/UIC are formed, which possess the final structure. When AN molecules are sufficient, the length of AN molecular arrays in urea canals increases as aging time prolonging until urea tunnels are saturated by AN.展开更多
The traditional alumina-silicate raw materials, for example, clays, in the precalcining technique of cement production, have been replaced by low grade and high silica content sandstones, shales, and industrial waste ...The traditional alumina-silicate raw materials, for example, clays, in the precalcining technique of cement production, have been replaced by low grade and high silica content sandstones, shales, and industrial waste residues, including fly ashes, slag, and others. The results are the change of compositions and characteristics of raw materials applied and a great effect on cement calcination process and clinker formation. In this work, the cement clinker formation process of different alumina-silicate raw materials to replace clay raw material was studied by chemical analysis, X-ray diffraction, differential thermal analysis, and high temperature microscope based on the characteristics of the alumina-silicate raw materials. The formation heat of the clinker was determined by the acid dissolution method. Influence of different alumina-silicate raw materials on the clinker burnability and formation process was studied. The results show that the changing of alumina- silicate raw materials, especially using industrial waste residues, can reduce the formation temperature of high temperature liquid phases, improve the burnability of raw materials, reduce the formation temperature and formation heat of clinker. And this study also observed the formation temperature and transformation of high temperature liquid phases in the heating process of raw materials by high temperature microscope.展开更多
Based on the Miedema＇s formation heat model for binary alloys and the Toop＇s asymmetric model for ternary alloys, the formation heat, excess entropy, and activity coefficients of silicon ranging from 1 900 K to 4 10...Based on the Miedema＇s formation heat model for binary alloys and the Toop＇s asymmetric model for ternary alloys, the formation heat, excess entropy, and activity coefficients of silicon ranging from 1 900 K to 4 100 K in the Fe-Si-C melt formed during the laser cladding high silicon coatings process were calculated. The results indicated that all values of lnγ^0Si, ε^CSi,ρ^SiSi and ρ^CSi are negative in the temperature range and these values increase as the temperature increases. And all values of ε^SiSi and ρ^Si-CSi are positive and these values decrease with increasing temperature. The iso-activity lines of silicon are distributed axisymmetrically to the incident laser beam in the melt pool vertical to the laser scanning direction. And the iso-activity lines of silicon in the front of the melt pool along the laser scanning direction are more intensive than those in the back of the melt pool. The activity of silicon on the bottom of the melt pool is lower than that in the effecting center of laser beam on the top surface of the melt pool and it may be the important reason for the formation of the silicides and excellent metallurgical bonding between the laser cladding coating and the substrate.展开更多
The molecular structures, infrared spectra, heats of formation （HOFs）, detonation proper- ties, chemical and thermal stabilities of several tetrahydro-[1,4]dioxino[2,3-d：5,6-d＇] diimida- zole derivatives with diff...The molecular structures, infrared spectra, heats of formation （HOFs）, detonation proper- ties, chemical and thermal stabilities of several tetrahydro-[1,4]dioxino[2,3-d：5,6-d＇] diimida- zole derivatives with different substituents were studied using DFT-B3LYP method. The properties of the compounds with different groups such as -NO2, -NH2, -N3, and -ONO2 were further compared. The -NO2 and -ONO2 groups are effective substituents for in- creasing the densities of the compounds, while the substitution of -N3 group can produce the largest HOF. The compound with -NO2 group has the same detonation properties as 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, while the compound with -ONO2 group has lower detonation properties than those of hexahydro-1,3,5-trinitro-l,3,5-triazine. The na- ture bond orbital analysis reveals that the relatively weak bonds in the molecules are the bonds between substituent groups and the molecular skeletons as well as C-O bonds in the dioxin rings. The electron withdrawing groups （-NO2, -N3, and -ONO2） have induc- rive effects on the linkages between the groups and molecular skeletons. In addition, re- searches show that the electronegativities of the groups are related with the stabilities of the compounds. Considering detonation performance and thermal stability, the 1,5-dinitro-2,6- bis（trinitromethyl）-3a,4a,7a,8a-tetrahydro-[1,4]dioxino-[2,3-d：5,6-d＇] diimidazole satisfies the requirements of high energy density materials.展开更多
We show the results of first-principles calculations of structural,phonon,elastic,thermal and electronic properties of the Mg-X inter-metallics in their respective ground state phase and meta-stable phases at equilibr...We show the results of first-principles calculations of structural,phonon,elastic,thermal and electronic properties of the Mg-X inter-metallics in their respective ground state phase and meta-stable phases at equilibrium geometry and the studied pressure range.Phonon dispersion spectra for these compounds were investigated by using the linear response technique.The phonon spectra do not show any abnormality in their respective ground state phase.The respective ground states phases of the studied system remain stable within the studied pressure range.Electronic and thermodynamic properties were derived by analysis of the electronic structures and quasi-harmonic approximation.The mixed bonding character of the Mg-X intermetallics is revealed by Mg-X bonds,and it leads the metallic nature.Most of the contribution originated from X ions d like states at Fermi level compared to that of Mg ion in these intermetallics.In this work,we also predicted the melting temperature of these intermetallics and evaluated the Debye temperature by using elastic constants.展开更多
Using geometry optimization and DFT method at the B3LYP/6-31G* level for C20H10, an equilibrium geometry is identified to have the form of polyhedral hydrocarbon with five carbon-carbon single bonds linking two pentap...Using geometry optimization and DFT method at the B3LYP/6-31G* level for C20H10, an equilibrium geometry is identified to have the form of polyhedral hydrocarbon with five carbon-carbon single bonds linking two pentaprismane cages. Thus, C20H10 is a tri-cage molecule with three pentaprismane cages. Vibrational frequencies and infrared spectrum are computed at the same level. The heat of formation for this molecule has also been estimated in this paper.展开更多
Density functional theory calculations and structural minimization techniques have been employed to characterize the structural and electronic properties of [5,6]-heterofullerene-C58Sn-C2. Since the heterofullerene mo...Density functional theory calculations and structural minimization techniques have been employed to characterize the structural and electronic properties of [5,6]-heterofullerene-C58Sn-C2. Since the heterofullerene molecule CssSn has a nearly planar tetra-coordinated Sn atom on the skeleton of cage, it is a heterofullerene molecule with odd number of atoms and a novel molecule. Vibrational frequencies of the molecule have been calculated at the B3LYP/CEP-31G level of theory. The absence of imaginary vibrational frequency confirms that the molecule corresponds to a true minimum on the potential energy hypersurface, and its heat of formation was estimated in this study. Owing to the C2 symmetry of [5,6]-heterofullerene-C58Sn-C2, it is a chiral molecule.展开更多
SCF-MO-AM1 calculations have been per formed on 10 silacyclohex-ane-based liquid crystal compounds by energy gradient completed optimization. The stable configurations, electronic structures, heats of formation, dipol...SCF-MO-AM1 calculations have been per formed on 10 silacyclohex-ane-based liquid crystal compounds by energy gradient completed optimization. The stable configurations, electronic structures, heats of formation, dipole moments and ionization potentials of titled comPounds are first reported. The calculated results are.discussed relating to the classical organic electronic theory.展开更多
The molecule with Th symmetry is rare.A dodecahedrane-like molecule C12H12B8 with uncommon Th symmetry has been reported here.Density functional calculations and minimization techniques have been employed to character...The molecule with Th symmetry is rare.A dodecahedrane-like molecule C12H12B8 with uncommon Th symmetry has been reported here.Density functional calculations and minimization techniques have been employed to characterize its structural and electronic properties.Its geometry,electronic properties,vibrational frequencies and heat of formation have been calculated at the B3LYP/6-311＋G（d,p） level of theory.The absence of imaginary vibrational frequency confirms that it corresponds to true minimum on the potential energy hypersurface.Its vibrational bands in the IR intensity have been discussed and compared with future experimental identification.At the B3LYP/6-311＋G（d,p） level,the heat of formation has been calculated to be 720.9 kJ mol^-1 using the isodesmic reaction.According to this value,it is a potential high energy density molecule.展开更多
Geometries, energies, and vibrational frequencies for two C4N12O4 isomers with pagodane- and isopagodane-like structures have been calculated at the B3LYP/6-31G＊ level.Isomers 1 and 2 are of D2h and D2d symmetry, res...Geometries, energies, and vibrational frequencies for two C4N12O4 isomers with pagodane- and isopagodane-like structures have been calculated at the B3LYP/6-31G＊ level.Isomers 1 and 2 are of D2h and D2d symmetry, respectively. Heats of formation for the two C4N12O4 isomers have been estimated in this paper, indicating they would be reasonable candidates for high energy density materials.展开更多
Based on the full optimized molecular geometric structure at 6-311＋＋G＊＊ level,the density（ρ）,detonation velocity（D）,and detonation pressure（P） for a new furazan-based energetic macrocycle compound,hexakis[1...Based on the full optimized molecular geometric structure at 6-311＋＋G＊＊ level,the density（ρ）,detonation velocity（D）,and detonation pressure（P） for a new furazan-based energetic macrocycle compound,hexakis[1,2,5]oxadi-azole[3,4-c：3＇,4＇-e;3＇＇,4＇＇-g：3＇＇＇,4＇＇＇-k：3＇＇＇＇,4＇＇＇＇-m：3＇＇＇＇＇,4＇＇＇＇＇-o][1,2,9,10]-tetraazacyclohexadecine,were investigated to verify its capacity as high energy density material（HEDM）. The infrared spectrum was also predicted. The heat of formation（HOF） was calculated using designed isodesmic reaction. The calculation on the bond dissociation energies（BDEs） was done and the pyrolysis mechanism of the compound was studied. The result shows that the N3–O1 bond in the ring may be the weakest one and the ring cleavage is possible to happen in thermal decomposition. The condensed phase HOF and the crystal density were also calculated for the title compound. The detonation data show that it can be considered as a potential HEDM. These results would provide basic information for the molecular design of novel high energy materials.展开更多
Density functional theory calculations at the B3LYP/6-311G＊＊ level are performed to study the geometric and elec- tronic structures of a series of nitroaliphatic compounds. The heats of formation （HOF） are predict...Density functional theory calculations at the B3LYP/6-311G＊＊ level are performed to study the geometric and elec- tronic structures of a series of nitroaliphatic compounds. The heats of formation （HOF） are predicted through the designed isodesmic reactions. Thermal stabilities are evaluated via the homolytic bond dissociation energies （BDEs）. Further, the correlation is developed between impact sensitivity h50% and the ratio （BDE/E） of the weakest BDE to the total energy E containing zero point energy correction. In addition, the relative stability of the title compounds is evaluated based on the analysis of calculated Mulliken population and the energy gaps between the frontier orbitals. The calculated BDEs, HOFs, and energy gaps consistently indicate that compound 1,1,1,6,6,6-hexanitro-3-hexyne is the most unstable and the compound 3,3,4,4,-tetranitro-hexane is the most stable. These results provide basic information for the molecular design of novel high energetic density materials.展开更多
Some nitro-substituted triazole-furazan derivatives are considered as potential candidates for high energy density compounds through quantum chemical treatment. Their geometric and electronic structures,band gap,therm...Some nitro-substituted triazole-furazan derivatives are considered as potential candidates for high energy density compounds through quantum chemical treatment. Their geometric and electronic structures,band gap,thermodynamic properties and detonation properties were studied using the density functional theory at the B3 LYP /6- 311 ＋ G＊＊level. The calculated energy of explosion,density,and detonation properties of model compounds were comparable to 1,3,5-trinitro-1,3,5-triazinane（ RDX） and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane（ HMX）. The heats of formation and bond dissociation energy were also analysed to understand the nature of thermal stabilities and the trigger bond in the pyrolysis process.展开更多
To further test whether polynitriprismanes are capable of being potential high energy density materials （HEDMs）, extensive theoretical calculations were carried out to investigate on a series of polynitrotriprisman...To further test whether polynitriprismanes are capable of being potential high energy density materials （HEDMs）, extensive theoretical calculations were carried out to investigate on a series of polynitrotriprismanes （PNNPs）： C6H6-.（NO2）. （n=1-6） Heats of formation （HOFs）, strain energies （SE）, and disproportionation energy （DE） were obtained using B3LYP/6-311＋G（2df, 2p）//B3LYP/6-31G＊ method by designing different isodesmic reactions, respectively. Detonation properties of PNNPs were obtained by the well-known KAMLET-JACOBS equations, using the predicted densities （p） obtained by Monte Carlo method and HOFs. It is found that they increase as the number of nitro groups n varies from 1 to 6, and PNNPs with n〉4 have excellent detonation properties The relative stability and the pyrolysis mechanism of PNNPs were evaluated by the calculated bond dissociation energy （BDE）. The comparison of BDE suggests that rupturing the C--C bond is the trigger for thermolysis of PNNPs. The computed BDE for cleavage of C--C bond （88.5 kJ/mol） further demonstrates that only the hexa-nitrotriprismane can be considered to be the target of HEDMs.展开更多
The theoretical calculation of LaNi4Co, in which Co substituted for Ni at various sites, was performed by adopting the method of total energy based on the Density Functional Theory. The augmented plane wave function w...The theoretical calculation of LaNi4Co, in which Co substituted for Ni at various sites, was performed by adopting the method of total energy based on the Density Functional Theory. The augmented plane wave function was selected as a basis set in combination with Ultra-soft Pseudopotential technology. The geometry of LaNi5 was optimized and the parameters and properties of the structure were given. The theoretical results accord well with experiments. This method provides a theoretical approach for the structure prediction of such alloy. The calculations of total energy, electronic density of states and Mulliken population of LaNi4Co were carried out. The electronic structure of LaNi4Co and the change of the electronic structure due to the Co-substitution in LaNi5 alloy were analyzed from the calculated results. The stability of the alloy in which Ni was partially substituted by Co at various sites was compared and the factors controlling stability were discussed. The theoretical value of formation heat was calculated.展开更多
文摘This study presents a predictive model for condensed-phase heats of formation of metal-containing energetic complexes(MCECs)and energetic metal-organic frameworks(EMOFs),leveraging a dataset of 148 compounds.Using elemental composition,triazole rings,and metal presence,the model achieves high accuracy(R^(2)>0.94,mean absolute error(MAE)≈390 kJ/mol)for screening high-energy materials.It outperforms prior methods,particularly for polycyclic systems,offering a practical tool for safer design and risk assessment in defense and industrial applications.
基金financial support from the National Natural Science Foundation of China(Nos.52434006,52374151,and 51927808)。
文摘As mining activities expand deeper,deep high-temperature formations seriously threaten the future safe exploitation,while deep geothermal energy has great potential for development.Combining the formation cooling and geothermal mining in mines to establish a thermos-hydraulic coupling numerical model for fractured formation.The study investigates the formation heat transfer behaviour,heat recovery performance and thermal economic benefits influenced during the life cycle.The results show that the accumulation of cold energy during the cold storage phase induces a decline in formation temperature.The heat recovery phase is determined by the extent of the initial cold domain,which contracts inward from the edge and decelerates the heat recovery rate gradually.With groundwater velocity increases,the thermal regulation efficiency gradually increases,the production temperature decreases,while the effective radius and thermal power increase first and then decrease.The injected volume and temperature significantly affect,with higher injection temperatures slowing thermal recovery,and the thermal regulation efficiency is more sensitive to changes in formation permeability and thermal conductivity.The heat extraction performance is positively correlated with all factors.The levelized cost of electricity is estimated at 0.1203$/(kW·h)during the cold storage.During the heat recovery,annual profit is primarily driven by cooling benefits.
文摘A semi-empirical calculation of the heat of formation was applied to ternary system: La-Fe-Al,Fe-Ni-V and Cu-Pd-Si.The calculated values were compared with the experimental ones and the coincidence was satisfactory.This method is helpful to predict the stabilities of ternary compounds and solid solubility.
文摘The ionization energies （IEs） of cyclopropenylidene （c-C3H2）, propargylene （HCCCH） and propadienylidene （H2CCC） have been computed using the CCSD（T）/CBS method, which involves the approxixnation to the complete basis set （CBS） limit at the coupled cluster level with single and double excitations plus quasi-perturbative triple excitation effect （CCSD（T））. The zero-point vibrational energy correction, the core-valence electronic correction, the scalar relativistic effect and the high level correction beyond the CCSD（T） excitations have also been made in these calculations. The CCSD（T）/CBS values for the IN（c-C3H2） and IE（HCCCH） of 9.164, 8.987 eV are in good agreement with the experimental values of （9.15±0.03） and （8.96±0.04） eV. The CCSD（T）/CBS calculations yield the IE values of 10.477 and 10.388 eV for the ionization transitions H2CCC→H2CCC^＋ （^2A1, C2v） and H2CCC→H2CCC＋ （^2A＇, Cs）, respectively. On the basis of the Franek-Condon factor consideration, the IE of （10.43±0.02） eV determined in the previous single-photon ionization experiment most likely corresponds to the ionization threshold for the H2CCC→H2CCC^＋（^2A1, C2v） transition. Although the precision of the experimental IN measurements fpr c-C3H2, HCCCH, and H2CCC is insufficient to pin down the accuracy of the theoretical calculations to better than ±30 meV, the excellent agreement between the experimental and theoretical IE values observed in the present study indicates that the CCSD（T）/CBS calculations together with high-order correlation corrections are capable of yielding reliable IE predictions for simple hydrocarbon carbenes and bi-radicals. We have also reported the heats of formation at 0 K （△H^of0） and 298 K （△H^of298）for c-C3H2/c-C3H2^＋, HCCCH/HCCCH^＋, and H2CCC/H2CCC^＋, The available experimental △H^of0 and △H^of298 values for c-C3H2/c C3H2^＋, HCCCH/HCCCH^＋ are found to be in good accord with the CCSD（T）/CBS predictions after taking into account the experimental uncertainties.
文摘In this paper, the nonlinear stationary waves forced by topography and diabatic heating are investigated. It is pointed out that (1) the nonlinear interaction of different stationary waves forced only by topography might form dipole blocking in the atmosphere, this might explain the dipole blocking appeared in the Pacific and Atlantic regions; (2) the dipole blocking could not be caused by the nonlinear interaction of the different stationary waves forced by the diabatic heating alone; (3) the nonlinear interaction of the diffferent stationary waves forced by both topography and diabatic heating could initiate dipole blocking in the atmosphere. In winter, the dipole blocking mainly occurs in the west regions of the Pacific and the Atlantic, and the heat source over the western part of the two oceans is advantageous to the formation of dipole blocking in the west of two oceans. However, in summer, the dipole blocking could be formed in the east part of the two oceans, and the heat source over the eastern part of two continents is favourable for the formation of dipole blocking in the east regions of two oceans.
文摘The formation process and composition of the acrylonitrile/urea inclusion compounds （AN/UIC） with different aging times and AN/urea molar feed ratios are studied by differential scanning calorimetry （DSC） and X-ray diffraction （XRD）. It is suggested that DSC can determine the vip/host ratio and the heat of decomposition. Meanwhile, the vip/host ratio and heat of decomposition are obtained, which are 1.17 and 5361.53 J/mol, respec- tively. It is suggested AN molecules included in urea canal lattice may be packed flat against each other. It is found that the formation of AN/UIC depends on the aging time. XRD results reveal that once AN molecules enter urea lattice, AN/UIC are formed, which possess the final structure. When AN molecules are sufficient, the length of AN molecular arrays in urea canals increases as aging time prolonging until urea tunnels are saturated by AN.
基金Funded by the National Basic Research Program of China("973"Program)(No.2009CB623102)the National High Technology Research and Development Program of China("863"Program)(No.2013AA031602)
文摘The traditional alumina-silicate raw materials, for example, clays, in the precalcining technique of cement production, have been replaced by low grade and high silica content sandstones, shales, and industrial waste residues, including fly ashes, slag, and others. The results are the change of compositions and characteristics of raw materials applied and a great effect on cement calcination process and clinker formation. In this work, the cement clinker formation process of different alumina-silicate raw materials to replace clay raw material was studied by chemical analysis, X-ray diffraction, differential thermal analysis, and high temperature microscope based on the characteristics of the alumina-silicate raw materials. The formation heat of the clinker was determined by the acid dissolution method. Influence of different alumina-silicate raw materials on the clinker burnability and formation process was studied. The results show that the changing of alumina- silicate raw materials, especially using industrial waste residues, can reduce the formation temperature of high temperature liquid phases, improve the burnability of raw materials, reduce the formation temperature and formation heat of clinker. And this study also observed the formation temperature and transformation of high temperature liquid phases in the heating process of raw materials by high temperature microscope.
基金National Natural Science Foundation of China (50474084)
文摘Based on the Miedema＇s formation heat model for binary alloys and the Toop＇s asymmetric model for ternary alloys, the formation heat, excess entropy, and activity coefficients of silicon ranging from 1 900 K to 4 100 K in the Fe-Si-C melt formed during the laser cladding high silicon coatings process were calculated. The results indicated that all values of lnγ^0Si, ε^CSi,ρ^SiSi and ρ^CSi are negative in the temperature range and these values increase as the temperature increases. And all values of ε^SiSi and ρ^Si-CSi are positive and these values decrease with increasing temperature. The iso-activity lines of silicon are distributed axisymmetrically to the incident laser beam in the melt pool vertical to the laser scanning direction. And the iso-activity lines of silicon in the front of the melt pool along the laser scanning direction are more intensive than those in the back of the melt pool. The activity of silicon on the bottom of the melt pool is lower than that in the effecting center of laser beam on the top surface of the melt pool and it may be the important reason for the formation of the silicides and excellent metallurgical bonding between the laser cladding coating and the substrate.
文摘The molecular structures, infrared spectra, heats of formation （HOFs）, detonation proper- ties, chemical and thermal stabilities of several tetrahydro-[1,4]dioxino[2,3-d：5,6-d＇] diimida- zole derivatives with different substituents were studied using DFT-B3LYP method. The properties of the compounds with different groups such as -NO2, -NH2, -N3, and -ONO2 were further compared. The -NO2 and -ONO2 groups are effective substituents for in- creasing the densities of the compounds, while the substitution of -N3 group can produce the largest HOF. The compound with -NO2 group has the same detonation properties as 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, while the compound with -ONO2 group has lower detonation properties than those of hexahydro-1,3,5-trinitro-l,3,5-triazine. The na- ture bond orbital analysis reveals that the relatively weak bonds in the molecules are the bonds between substituent groups and the molecular skeletons as well as C-O bonds in the dioxin rings. The electron withdrawing groups （-NO2, -N3, and -ONO2） have induc- rive effects on the linkages between the groups and molecular skeletons. In addition, re- searches show that the electronegativities of the groups are related with the stabilities of the compounds. Considering detonation performance and thermal stability, the 1,5-dinitro-2,6- bis（trinitromethyl）-3a,4a,7a,8a-tetrahydro-[1,4]dioxino-[2,3-d：5,6-d＇] diimidazole satisfies the requirements of high energy density materials.
基金The present work was financially supported by a Grant-Aid for Science and Engineering Research Board(Grant No.SERB/F/922/2014-15),Department of Science&Technology,Government of India.
文摘We show the results of first-principles calculations of structural,phonon,elastic,thermal and electronic properties of the Mg-X inter-metallics in their respective ground state phase and meta-stable phases at equilibrium geometry and the studied pressure range.Phonon dispersion spectra for these compounds were investigated by using the linear response technique.The phonon spectra do not show any abnormality in their respective ground state phase.The respective ground states phases of the studied system remain stable within the studied pressure range.Electronic and thermodynamic properties were derived by analysis of the electronic structures and quasi-harmonic approximation.The mixed bonding character of the Mg-X intermetallics is revealed by Mg-X bonds,and it leads the metallic nature.Most of the contribution originated from X ions d like states at Fermi level compared to that of Mg ion in these intermetallics.In this work,we also predicted the melting temperature of these intermetallics and evaluated the Debye temperature by using elastic constants.
基金This work was supported by the Natural Science Foundation of Shandong Province (Y2002G11)
文摘Using geometry optimization and DFT method at the B3LYP/6-31G* level for C20H10, an equilibrium geometry is identified to have the form of polyhedral hydrocarbon with five carbon-carbon single bonds linking two pentaprismane cages. Thus, C20H10 is a tri-cage molecule with three pentaprismane cages. Vibrational frequencies and infrared spectrum are computed at the same level. The heat of formation for this molecule has also been estimated in this paper.
基金supported by the Natural Science Foundation Committee of China (No. 60671010)
文摘Density functional theory calculations and structural minimization techniques have been employed to characterize the structural and electronic properties of [5,6]-heterofullerene-C58Sn-C2. Since the heterofullerene molecule CssSn has a nearly planar tetra-coordinated Sn atom on the skeleton of cage, it is a heterofullerene molecule with odd number of atoms and a novel molecule. Vibrational frequencies of the molecule have been calculated at the B3LYP/CEP-31G level of theory. The absence of imaginary vibrational frequency confirms that the molecule corresponds to a true minimum on the potential energy hypersurface, and its heat of formation was estimated in this study. Owing to the C2 symmetry of [5,6]-heterofullerene-C58Sn-C2, it is a chiral molecule.
文摘SCF-MO-AM1 calculations have been per formed on 10 silacyclohex-ane-based liquid crystal compounds by energy gradient completed optimization. The stable configurations, electronic structures, heats of formation, dipole moments and ionization potentials of titled comPounds are first reported. The calculated results are.discussed relating to the classical organic electronic theory.
基金supported by the Natural Science Foundation of Shandong Province (No. ZR2011BM022)
文摘The molecule with Th symmetry is rare.A dodecahedrane-like molecule C12H12B8 with uncommon Th symmetry has been reported here.Density functional calculations and minimization techniques have been employed to characterize its structural and electronic properties.Its geometry,electronic properties,vibrational frequencies and heat of formation have been calculated at the B3LYP/6-311＋G（d,p） level of theory.The absence of imaginary vibrational frequency confirms that it corresponds to true minimum on the potential energy hypersurface.Its vibrational bands in the IR intensity have been discussed and compared with future experimental identification.At the B3LYP/6-311＋G（d,p） level,the heat of formation has been calculated to be 720.9 kJ mol^-1 using the isodesmic reaction.According to this value,it is a potential high energy density molecule.
基金This work was supported by the Natural Science Foundation of Shandong Province (Y2002G11)
文摘Geometries, energies, and vibrational frequencies for two C4N12O4 isomers with pagodane- and isopagodane-like structures have been calculated at the B3LYP/6-31G＊ level.Isomers 1 and 2 are of D2h and D2d symmetry, respectively. Heats of formation for the two C4N12O4 isomers have been estimated in this paper, indicating they would be reasonable candidates for high energy density materials.
基金supported by the National Natural Science Foundation of China(No.U1304111)the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.14HASTIT039)the Innovation Team of Henan University of Science and Technology(2015XTD001)
文摘Based on the full optimized molecular geometric structure at 6-311＋＋G＊＊ level,the density（ρ）,detonation velocity（D）,and detonation pressure（P） for a new furazan-based energetic macrocycle compound,hexakis[1,2,5]oxadi-azole[3,4-c：3＇,4＇-e;3＇＇,4＇＇-g：3＇＇＇,4＇＇＇-k：3＇＇＇＇,4＇＇＇＇-m：3＇＇＇＇＇,4＇＇＇＇＇-o][1,2,9,10]-tetraazacyclohexadecine,were investigated to verify its capacity as high energy density material（HEDM）. The infrared spectrum was also predicted. The heat of formation（HOF） was calculated using designed isodesmic reaction. The calculation on the bond dissociation energies（BDEs） was done and the pyrolysis mechanism of the compound was studied. The result shows that the N3–O1 bond in the ring may be the weakest one and the ring cleavage is possible to happen in thermal decomposition. The condensed phase HOF and the crystal density were also calculated for the title compound. The detonation data show that it can be considered as a potential HEDM. These results would provide basic information for the molecular design of novel high energy materials.
基金supported by the National Natural Science Foundation of China(Grant Nos.11304022 and11347010)the Research Foundation of Education Bureau of Hubei Province,China(Grant Nos.Q20131208,T201204,and XD2014069)+1 种基金the Foundation of Yangtze University for Outstanding Young Teachers,China(Grant Nos.cyq201321 and cyq201322)the Project for Basic Subjects(Grant No.2013cjp10)
文摘Density functional theory calculations at the B3LYP/6-311G＊＊ level are performed to study the geometric and elec- tronic structures of a series of nitroaliphatic compounds. The heats of formation （HOF） are predicted through the designed isodesmic reactions. Thermal stabilities are evaluated via the homolytic bond dissociation energies （BDEs）. Further, the correlation is developed between impact sensitivity h50% and the ratio （BDE/E） of the weakest BDE to the total energy E containing zero point energy correction. In addition, the relative stability of the title compounds is evaluated based on the analysis of calculated Mulliken population and the energy gaps between the frontier orbitals. The calculated BDEs, HOFs, and energy gaps consistently indicate that compound 1,1,1,6,6,6-hexanitro-3-hexyne is the most unstable and the compound 3,3,4,4,-tetranitro-hexane is the most stable. These results provide basic information for the molecular design of novel high energetic density materials.
文摘Some nitro-substituted triazole-furazan derivatives are considered as potential candidates for high energy density compounds through quantum chemical treatment. Their geometric and electronic structures,band gap,thermodynamic properties and detonation properties were studied using the density functional theory at the B3 LYP /6- 311 ＋ G＊＊level. The calculated energy of explosion,density,and detonation properties of model compounds were comparable to 1,3,5-trinitro-1,3,5-triazinane（ RDX） and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane（ HMX）. The heats of formation and bond dissociation energy were also analysed to understand the nature of thermal stabilities and the trigger bond in the pyrolysis process.
基金Projects(2006DFA41090,2007DFA40680) supported by the International Cooperation Project on Traditional Chinese Medicines of Ministry of Science and Technology of ChinaProject(20475066) supported by the National Natural Science Foundation of China
文摘To further test whether polynitriprismanes are capable of being potential high energy density materials （HEDMs）, extensive theoretical calculations were carried out to investigate on a series of polynitrotriprismanes （PNNPs）： C6H6-.（NO2）. （n=1-6） Heats of formation （HOFs）, strain energies （SE）, and disproportionation energy （DE） were obtained using B3LYP/6-311＋G（2df, 2p）//B3LYP/6-31G＊ method by designing different isodesmic reactions, respectively. Detonation properties of PNNPs were obtained by the well-known KAMLET-JACOBS equations, using the predicted densities （p） obtained by Monte Carlo method and HOFs. It is found that they increase as the number of nitro groups n varies from 1 to 6, and PNNPs with n〉4 have excellent detonation properties The relative stability and the pyrolysis mechanism of PNNPs were evaluated by the calculated bond dissociation energy （BDE）. The comparison of BDE suggests that rupturing the C--C bond is the trigger for thermolysis of PNNPs. The computed BDE for cleavage of C--C bond （88.5 kJ/mol） further demonstrates that only the hexa-nitrotriprismane can be considered to be the target of HEDMs.
文摘The theoretical calculation of LaNi4Co, in which Co substituted for Ni at various sites, was performed by adopting the method of total energy based on the Density Functional Theory. The augmented plane wave function was selected as a basis set in combination with Ultra-soft Pseudopotential technology. The geometry of LaNi5 was optimized and the parameters and properties of the structure were given. The theoretical results accord well with experiments. This method provides a theoretical approach for the structure prediction of such alloy. The calculations of total energy, electronic density of states and Mulliken population of LaNi4Co were carried out. The electronic structure of LaNi4Co and the change of the electronic structure due to the Co-substitution in LaNi5 alloy were analyzed from the calculated results. The stability of the alloy in which Ni was partially substituted by Co at various sites was compared and the factors controlling stability were discussed. The theoretical value of formation heat was calculated.
