A full-dimensional analytical potential energy surface （APES） for the F ＋ CH4 →HF ＋ CH3 reaction is developed based on 7127 ab initio energy points at the unrestricted coupled-cluster with single, double, and per...A full-dimensional analytical potential energy surface （APES） for the F ＋ CH4 →HF ＋ CH3 reaction is developed based on 7127 ab initio energy points at the unrestricted coupled-cluster with single, double, and perturbative triple excitations. The correlation-consistent polarized triple-split valence basis set is used. The APES is represented with a many-body expansion containing 239 parameters determined by the least square fitting method. The two-body terms of the APES are fitted by potential energy curves with multi-reference configuration interaction, which can describe the diatomic molecules （CH, H2, HF, and CF） accurately. It is found that the APES can reproduce the geometry and vibrational frequencies of the saddle point better than those available in the literature. The rate constants based on the present APES support the experimental results of Moore et al. [Int. J. Chem. Kin. 26, 813 （1994）]. The analytical first-order derivation of energy is also provided, making the present APES convenient and efficient for investigating the title reaction with quasiclassical trajectory calculations.展开更多
Calculation of total energies of the electronic ground states of atoms forms the basis for the frozen-core pseudopotentials used in atomistic calculations of much larger scale. Reference values for these energies prov...Calculation of total energies of the electronic ground states of atoms forms the basis for the frozen-core pseudopotentials used in atomistic calculations of much larger scale. Reference values for these energies provide a benchmark for the validation of new software to calculate such potentials. In addition, basic atomic-scale electronic properties such as the (first) ionization energy provide a simple check on the approximation used in the calculation method. We present a comparison of the total energies and ionization energies of atoms Z = 1 - 92 calculated in density functional theory with several levels of exchange-correlation functional and the Hartree-Fock method, comparing ionization energies to experiment. We also investigate the role of relativistic treatment on these energies.展开更多
Fe-Cr ferritic/martensitic(F/M)steels have been proposed as one of the candidate materials for the Generation IV nuclear technologies.In this study,a widely-used ferritic/martensitic steel,T91 steel,was irradiated by ...Fe-Cr ferritic/martensitic(F/M)steels have been proposed as one of the candidate materials for the Generation IV nuclear technologies.In this study,a widely-used ferritic/martensitic steel,T91 steel,was irradiated by 196-MeV Kr^(+)ions at 550℃.To reveal the irradiation mechanism,the microstructure evolution of irradiated T91 steel was studied in details by transmission electron microscope(TEM).With increasing dose,the defects gradually changed from black dots to dislocation loops,and further to form dislocation walls near grain boundaries due to the production of a large number of dislocations.When many dislocation loops of primary a0/2<111>type with high migration interacted with other defects or carbon atoms,it led to the production of dislocation segments and other dislocation loops of a0<100>type.Lots of defects accumulated near grain boundaries in the irradiated area,especially in the high-dose area.The grain boundaries of martensite laths acted as important sinks of irradiation defects in T91.Elevated temperature facilitated the migration of defects,leading to the accumulation of defects near the grain boundaries of martensite laths.展开更多
A cryogenic scanning electron microscopy（cryo-SEM） technique was used to explore the shear-thickening behavior of Fe-ZSM5 zeolite pastes and to discover its underlying mechanism. Bare Fe-ZSM5 zeolite samples were fo...A cryogenic scanning electron microscopy（cryo-SEM） technique was used to explore the shear-thickening behavior of Fe-ZSM5 zeolite pastes and to discover its underlying mechanism. Bare Fe-ZSM5 zeolite samples were found to contain agglomerations, which may break the flow of the pastes and cause shear-thickening behaviors. However, the shear-thickening behaviors can be eliminated by the addition of halloysite and various boehmites because of improved particle packing. Furthermore, compared with pure Fe-ZSM5 zeolite samples and its composite samples with halloysite, the samples with boehmite（Pural SB or Disperal） additions exhibited network structures in their cryo-SEM images; these structures could facilitate the storage and release of flow water, smooth paste flow, and avoid shear-thickening. By contrast, another boehmite（Versal 250） formed agglomerations rather than network structures after being added to the Fe-ZSM5 zeolite paste and resulted in shear-thickening behavior. Consequently, the results suggest that these network structures play key roles in eliminating the shear-thickening behavior.展开更多
The work described in this paper is a study of gold adsorption on the whole tip surface of iridium field emitter. The study has been carried out using field emission microscope. Changes in electron work function of th...The work described in this paper is a study of gold adsorption on the whole tip surface of iridium field emitter. The study has been carried out using field emission microscope. Changes in electron work function of the iridium substrate which are produced by vapor of deposition of submonolayers of gold in ultra high vacuum have been measured by noting the changes in the slope of Fowler-Nordheim plots. The same procedure for studying the adsorption of copper on iridium?[1] was followed to study the adsorption of gold on iridium. Adsorption of gold was examined on the iridium surface containing the (100) ring which could not be removed thermally.展开更多
An ab initio analytical potential energy surface called BW3 for the CIH2 reactive system is presented. The fit of this surface is based on about 1 200 ab initio energy points, computed with multi-reference configurati...An ab initio analytical potential energy surface called BW3 for the CIH2 reactive system is presented. The fit of this surface is based on about 1 200 ab initio energy points, computed with multi-reference configuration interaction(MRCI) and scaling external correlation (SEC) method and a very large basis set. The precision in the fit is very high. The BW3 surface could reproduce correctly the dissociation energy of H2 and HCI, and the endothermicity of the Cl + H2 abstraction reaction. For the Cl + H2 abstraction reaction, the saddle point of BW3 lies in collinear geometries, and the barrier height is 32.84 kJ/mol; for the H + CIH exchange reaction, the barrier of BW3 is also linear, with a height of 77.40 kJ/mol.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos. 11174117 and 10974078)
文摘A full-dimensional analytical potential energy surface （APES） for the F ＋ CH4 →HF ＋ CH3 reaction is developed based on 7127 ab initio energy points at the unrestricted coupled-cluster with single, double, and perturbative triple excitations. The correlation-consistent polarized triple-split valence basis set is used. The APES is represented with a many-body expansion containing 239 parameters determined by the least square fitting method. The two-body terms of the APES are fitted by potential energy curves with multi-reference configuration interaction, which can describe the diatomic molecules （CH, H2, HF, and CF） accurately. It is found that the APES can reproduce the geometry and vibrational frequencies of the saddle point better than those available in the literature. The rate constants based on the present APES support the experimental results of Moore et al. [Int. J. Chem. Kin. 26, 813 （1994）]. The analytical first-order derivation of energy is also provided, making the present APES convenient and efficient for investigating the title reaction with quasiclassical trajectory calculations.
文摘Calculation of total energies of the electronic ground states of atoms forms the basis for the frozen-core pseudopotentials used in atomistic calculations of much larger scale. Reference values for these energies provide a benchmark for the validation of new software to calculate such potentials. In addition, basic atomic-scale electronic properties such as the (first) ionization energy provide a simple check on the approximation used in the calculation method. We present a comparison of the total energies and ionization energies of atoms Z = 1 - 92 calculated in density functional theory with several levels of exchange-correlation functional and the Hartree-Fock method, comparing ionization energies to experiment. We also investigate the role of relativistic treatment on these energies.
基金Project supported by Guangdong Major Project of Basic and Applied Basic Research(Grant No.2019B030302011)the National Natural Science Foundation of China(Grant Nos.U2032143,11902370,and 52005523)+2 种基金the International Science and Technology Cooperation Program of Guangdong Province,China(Grant No.2019A050510022)the China Postdoctoral Science Foundation(Grant Nos.2019M653173 and 2019TQ0374)the Heavy Ion Research Facility of Lanzhou(HIRFL).
文摘Fe-Cr ferritic/martensitic(F/M)steels have been proposed as one of the candidate materials for the Generation IV nuclear technologies.In this study,a widely-used ferritic/martensitic steel,T91 steel,was irradiated by 196-MeV Kr^(+)ions at 550℃.To reveal the irradiation mechanism,the microstructure evolution of irradiated T91 steel was studied in details by transmission electron microscope(TEM).With increasing dose,the defects gradually changed from black dots to dislocation loops,and further to form dislocation walls near grain boundaries due to the production of a large number of dislocations.When many dislocation loops of primary a0/2<111>type with high migration interacted with other defects or carbon atoms,it led to the production of dislocation segments and other dislocation loops of a0<100>type.Lots of defects accumulated near grain boundaries in the irradiated area,especially in the high-dose area.The grain boundaries of martensite laths acted as important sinks of irradiation defects in T91.Elevated temperature facilitated the migration of defects,leading to the accumulation of defects near the grain boundaries of martensite laths.
基金financially supported by the National Natural Science Foundation of China (No. 51602018)Beijing Natural Science Foundation (No. 2154052)+2 种基金China Postdoctoral Science Foundation Funded Project (No. 2014M560044)the Fundamental Research Funds for the Central Universities (FRF-GF-17-B7)National Key Technologies Research and Development Program of China:Key International Science and Technology Cooperation Projects (2016YFE0111500)
文摘A cryogenic scanning electron microscopy（cryo-SEM） technique was used to explore the shear-thickening behavior of Fe-ZSM5 zeolite pastes and to discover its underlying mechanism. Bare Fe-ZSM5 zeolite samples were found to contain agglomerations, which may break the flow of the pastes and cause shear-thickening behaviors. However, the shear-thickening behaviors can be eliminated by the addition of halloysite and various boehmites because of improved particle packing. Furthermore, compared with pure Fe-ZSM5 zeolite samples and its composite samples with halloysite, the samples with boehmite（Pural SB or Disperal） additions exhibited network structures in their cryo-SEM images; these structures could facilitate the storage and release of flow water, smooth paste flow, and avoid shear-thickening. By contrast, another boehmite（Versal 250） formed agglomerations rather than network structures after being added to the Fe-ZSM5 zeolite paste and resulted in shear-thickening behavior. Consequently, the results suggest that these network structures play key roles in eliminating the shear-thickening behavior.
文摘The work described in this paper is a study of gold adsorption on the whole tip surface of iridium field emitter. The study has been carried out using field emission microscope. Changes in electron work function of the iridium substrate which are produced by vapor of deposition of submonolayers of gold in ultra high vacuum have been measured by noting the changes in the slope of Fowler-Nordheim plots. The same procedure for studying the adsorption of copper on iridium?[1] was followed to study the adsorption of gold on iridium. Adsorption of gold was examined on the iridium surface containing the (100) ring which could not be removed thermally.
文摘An ab initio analytical potential energy surface called BW3 for the CIH2 reactive system is presented. The fit of this surface is based on about 1 200 ab initio energy points, computed with multi-reference configuration interaction(MRCI) and scaling external correlation (SEC) method and a very large basis set. The precision in the fit is very high. The BW3 surface could reproduce correctly the dissociation energy of H2 and HCI, and the endothermicity of the Cl + H2 abstraction reaction. For the Cl + H2 abstraction reaction, the saddle point of BW3 lies in collinear geometries, and the barrier height is 32.84 kJ/mol; for the H + CIH exchange reaction, the barrier of BW3 is also linear, with a height of 77.40 kJ/mol.
