The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulati...The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures.AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased.Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction.The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels.We provided explanations consistent with the principles of thermodynamics and statistical physics.The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments.展开更多
Vanadium oxide clusters VxOy^q（x≤8, q=0, ±1） are classified according to the oxidation index （△=2y＋q-5x） of each cluster. Density functional calculations indicate that clusters with the same oxidation inde...Vanadium oxide clusters VxOy^q（x≤8, q=0, ±1） are classified according to the oxidation index （△=2y＋q-5x） of each cluster. Density functional calculations indicate that clusters with the same oxidation index tend to have similar bonding characters, electronic structures, and reactivities. This general rule leads to the findings of new possible ground state struc- tures for V206 and V3O6＋ clusters. This successful application of the classification method on vanadium oxide clusters proves that this method is very effective in studying the bonding properties of early transition metal oxide clusters.展开更多
We have investigated the effect of surface dangling bonds and molecular passivation on the doping of GaAs nanowires by first-principles calculations. Results show that the positively charged surface dangling bond on G...We have investigated the effect of surface dangling bonds and molecular passivation on the doping of GaAs nanowires by first-principles calculations. Results show that the positively charged surface dangling bond on Ga atom is the most stable defect for both ultrathin and large size GaAs nanowires. It can form the trap centers of holes and then prefer to capture the holes from p-type doping. Thus it could obviously reduce the efficiency of the p-type doping. We also found that the NO2 molecule is electronegative enough to capture the unpaired electrons of surface dangling bonds, which is an ideal passivation material for the Zn-doped GaAs nanowires.展开更多
The multi-scale expression of enormously complicated laneway data requires differentiation of both contents and the way the contents are expressed. To accomplish multi-scale expression laneway data must support multi-...The multi-scale expression of enormously complicated laneway data requires differentiation of both contents and the way the contents are expressed. To accomplish multi-scale expression laneway data must support multi-scale transformation and have consistent topological relationships. Although the laneway data generated by traverse survey-ing is non-scale data it is still impossible to construct a multi-scale spatial database directly from it. In this paper an al-gorithm is presented to first calculate the laneway mid-line to support multi-scale transformation; then to express topo-logical relationships arising from the data structure; and,finally,a laneway spatial database is built and multi-scale ex-pression is achieved using components GIS-SuperMap Objects. The research result is of great significance for improv-ing the efficiency of laneway data storage and updating,for ensuring consistency of laneway data expression and for extending the potential value of a mine spatial database.展开更多
Heterogenization of organic-macrocyclic metal catalysts is one of the simplest and most efficient methods for effective separation of products and cyclic application of a catalyst.By using an environmentally friendly ...Heterogenization of organic-macrocyclic metal catalysts is one of the simplest and most efficient methods for effective separation of products and cyclic application of a catalyst.By using an environmentally friendly Mn-corrolazine catalyst as the building unit,which can directly oxidize organic substrates under oxygen atmosphere and mild conditions,we theoretically constructed a novel two-dimensional(2D)Mn-corrolazine nanocatalytic material with high catalytic activity.In this material,each Mn atom maintains its electronic configuration in the monomer and can directly activate O2 as the single-atom catalyst(SAC)center to form a radical-like[Mn]-O-O under mild visible-light irradiation conditions.The newly generated[Mn]–O–O can efficiently and selectively oxidize C–H bonds to form alcohol species through H-abstraction and the rebound reaction.Moreover,the catalytic reaction is easily regulated by an external electric field along its intrinsic Mn–O–O reaction axis.The current study provides a theoretical foundation for further experimental studies and practical applications of the Mn-corrolazine-based SAC.展开更多
The C--C bond dissociation energy （BDE） is a very important data in research of hydrocarbon cracking reactions, because it reflects the difficulty level of chemical reactions. But it is very difficult to obtain the ...The C--C bond dissociation energy （BDE） is a very important data in research of hydrocarbon cracking reactions, because it reflects the difficulty level of chemical reactions. But it is very difficult to obtain the C--C bond dissociation energy （BDE） by experiments, so using quantum chemistry calculation such as density functional theory （DFT） to study the C--C bond dissociation energy is a very useful means. The impact of acceptor substituents and donor substituents on the C--C bond length distribution was studied.展开更多
Most of modern systems for information retrieval, fusion and management have to deal with more and more qualitative information （by linguistic labels） besides information expressed quantitatively （by numbers）, sin...Most of modern systems for information retrieval, fusion and management have to deal with more and more qualitative information （by linguistic labels） besides information expressed quantitatively （by numbers）, since human reports are better and easier expressed in natural language than with numbers. In this paper, Herrera-Martfnez＇s 2-Tuple linguistic representation model is extended for reasoning with uncertain and qualitative information in Dezert-Smarandache Theory （DSmT） framework, in order to overcome the limitations of current approaches, i.e., the lack of precision in the final results of linguistic information fusion according to 1-Tuple representation （ q1 ）- The linguistic information which expresses the expert＇s qualitative beliefs is expressed by means of mixed 2 Tuples （equidistant linguistic labels with a numeric biased value）. Together with the 2-Tuple representation model, some basic operators are presented to carry out the fusion operation among qualitative information sources. At last, through simple example how 2-Tuple qualitative DSmT-based （q2 DSmT） fusion rules can be used for qualitative reasoning and fusion under uncertainty, which advantage is also showed by comparing with other methods.展开更多
In recent years, a number of organisations have implemented Executive Information Systems （EIS） including Computer-Based Information Systems （CBIS） in order to improve the performance of their executives＇ jobs th...In recent years, a number of organisations have implemented Executive Information Systems （EIS） including Computer-Based Information Systems （CBIS） in order to improve the performance of their executives＇ jobs though the majority of executives are unwilling to use EIS applications because of their design defects. Present researches on Executive Information Systems （EIS） are limited and less focused on the factors associated with EIS successful usage. This research adopts an extension of the Technology Acceptance Model （TAM） to derive useful variables to address the problem of the low usage of EIS by executives due to social factors, habits and facilitation conditions variables in Triandis＇ Framework. It reports on the adoption and usage of EIS by the executives in Organizations. The results show that experience in EIS usage was high with most respondents having used EIS for between 0 to 4 years （72.41%）, followed by the 5-9 years group with 25.86%. However, in terms of ability to use EIS, most executives were at the expert （knowledgeable）, casual user with 37.93%, followed by novice frequent user group with 31.03%. From this research, the authors propose a model that incorporates the habits, social factors and facilitating conditions in an Executive Information Systems.展开更多
The electronic structures,chemical bonding,elastic and optical properties of the novel hP24 phase WB3 were investigated by using density-functional theory(DFT) within generalized gradient approximation(GGA).The calcul...The electronic structures,chemical bonding,elastic and optical properties of the novel hP24 phase WB3 were investigated by using density-functional theory(DFT) within generalized gradient approximation(GGA).The calculated energy band structures show that the hP24 phase WB3 is metallic material.The density of state(DOS) and the partial density of state(PDOS) calculations show that the DOS near the Fermi level is mainly from the W 5d and B 2p states.Population analysis suggests that the chemical bonding in hP24-WB3 has predominantly covalent characteristics with mixed covalent-ionic characteristics.Basic physical properties,such as lattice constant,bulk modulus,shear modulus and elastic constants Cij were calculated.The elastic modulus E and Poisson ratio υ were also predicted.The results show that hP24-WB3 phase is mechanically stable and behaves in a brittle manner.Detailed analysis of all optical functions reveals that WB3 is a better dielectric material,and reflectivity spectra show that WB3 can be promised as good coating material in the energy regions of 8.5-11.4 eV and 14.5-15.5 eV.展开更多
Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional th...Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional theory calculation at wB97XD/6-31G（d） level. Strong interaction between porphyrin and heterofullerene moiety was predicted for these complexes based on geometry and electronic structure analysis. Especially, pseudobonding interaction occurring between the B atom of fullerene and the N atom of porphyrin was predicted to occur in C59B-ZnP complex, but be broken in C59B-ZnP complex. Time-dependent density functional theory calculation manifests the redshift of electron absorption for ZnP upon the interaction with heterofullerene.展开更多
文摘The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures.AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased.Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction.The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels.We provided explanations consistent with the principles of thermodynamics and statistical physics.The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments.
基金This work was supported by the Hundred Talents Fund of the Chinese Academy of Sciences and the National Natural Science Foundation of China （No.20803083 and No.20933008）.
文摘Vanadium oxide clusters VxOy^q（x≤8, q=0, ±1） are classified according to the oxidation index （△=2y＋q-5x） of each cluster. Density functional calculations indicate that clusters with the same oxidation index tend to have similar bonding characters, electronic structures, and reactivities. This general rule leads to the findings of new possible ground state struc- tures for V206 and V3O6＋ clusters. This successful application of the classification method on vanadium oxide clusters proves that this method is very effective in studying the bonding properties of early transition metal oxide clusters.
基金This work was supported by the National Basic Research Program of China （No.2010CB327600）, the National Natural Science Foundation of China （No.61020106007 and No.61376019）, the Natural Science Foundation of Beijing （No.4142038）, the Specialized Research Fund for the Doctoral Program of Higher Education （No.20120005110011）, and the 111 Program of China （No.B07005）. Jian-gong Cui would like to thank Dr. Xin Yan and Dr. Jun-shuai Li from Beijing University of Posts and Telecommunications for useful discussions.
文摘We have investigated the effect of surface dangling bonds and molecular passivation on the doping of GaAs nanowires by first-principles calculations. Results show that the positively charged surface dangling bond on Ga atom is the most stable defect for both ultrathin and large size GaAs nanowires. It can form the trap centers of holes and then prefer to capture the holes from p-type doping. Thus it could obviously reduce the efficiency of the p-type doping. We also found that the NO2 molecule is electronegative enough to capture the unpaired electrons of surface dangling bonds, which is an ideal passivation material for the Zn-doped GaAs nanowires.
基金Project 2005B018 supported by the Science Foundation of China University of Mining and Technology
文摘The multi-scale expression of enormously complicated laneway data requires differentiation of both contents and the way the contents are expressed. To accomplish multi-scale expression laneway data must support multi-scale transformation and have consistent topological relationships. Although the laneway data generated by traverse survey-ing is non-scale data it is still impossible to construct a multi-scale spatial database directly from it. In this paper an al-gorithm is presented to first calculate the laneway mid-line to support multi-scale transformation; then to express topo-logical relationships arising from the data structure; and,finally,a laneway spatial database is built and multi-scale ex-pression is achieved using components GIS-SuperMap Objects. The research result is of great significance for improv-ing the efficiency of laneway data storage and updating,for ensuring consistency of laneway data expression and for extending the potential value of a mine spatial database.
文摘Heterogenization of organic-macrocyclic metal catalysts is one of the simplest and most efficient methods for effective separation of products and cyclic application of a catalyst.By using an environmentally friendly Mn-corrolazine catalyst as the building unit,which can directly oxidize organic substrates under oxygen atmosphere and mild conditions,we theoretically constructed a novel two-dimensional(2D)Mn-corrolazine nanocatalytic material with high catalytic activity.In this material,each Mn atom maintains its electronic configuration in the monomer and can directly activate O2 as the single-atom catalyst(SAC)center to form a radical-like[Mn]-O-O under mild visible-light irradiation conditions.The newly generated[Mn]–O–O can efficiently and selectively oxidize C–H bonds to form alcohol species through H-abstraction and the rebound reaction.Moreover,the catalytic reaction is easily regulated by an external electric field along its intrinsic Mn–O–O reaction axis.The current study provides a theoretical foundation for further experimental studies and practical applications of the Mn-corrolazine-based SAC.
文摘The C--C bond dissociation energy （BDE） is a very important data in research of hydrocarbon cracking reactions, because it reflects the difficulty level of chemical reactions. But it is very difficult to obtain the C--C bond dissociation energy （BDE） by experiments, so using quantum chemistry calculation such as density functional theory （DFT） to study the C--C bond dissociation energy is a very useful means. The impact of acceptor substituents and donor substituents on the C--C bond length distribution was studied.
基金Supported by the National Natural Science Foundation of China (60804063)863 Program (2006AA040202)
文摘Most of modern systems for information retrieval, fusion and management have to deal with more and more qualitative information （by linguistic labels） besides information expressed quantitatively （by numbers）, since human reports are better and easier expressed in natural language than with numbers. In this paper, Herrera-Martfnez＇s 2-Tuple linguistic representation model is extended for reasoning with uncertain and qualitative information in Dezert-Smarandache Theory （DSmT） framework, in order to overcome the limitations of current approaches, i.e., the lack of precision in the final results of linguistic information fusion according to 1-Tuple representation （ q1 ）- The linguistic information which expresses the expert＇s qualitative beliefs is expressed by means of mixed 2 Tuples （equidistant linguistic labels with a numeric biased value）. Together with the 2-Tuple representation model, some basic operators are presented to carry out the fusion operation among qualitative information sources. At last, through simple example how 2-Tuple qualitative DSmT-based （q2 DSmT） fusion rules can be used for qualitative reasoning and fusion under uncertainty, which advantage is also showed by comparing with other methods.
文摘In recent years, a number of organisations have implemented Executive Information Systems （EIS） including Computer-Based Information Systems （CBIS） in order to improve the performance of their executives＇ jobs though the majority of executives are unwilling to use EIS applications because of their design defects. Present researches on Executive Information Systems （EIS） are limited and less focused on the factors associated with EIS successful usage. This research adopts an extension of the Technology Acceptance Model （TAM） to derive useful variables to address the problem of the low usage of EIS by executives due to social factors, habits and facilitation conditions variables in Triandis＇ Framework. It reports on the adoption and usage of EIS by the executives in Organizations. The results show that experience in EIS usage was high with most respondents having used EIS for between 0 to 4 years （72.41%）, followed by the 5-9 years group with 25.86%. However, in terms of ability to use EIS, most executives were at the expert （knowledgeable）, casual user with 37.93%, followed by novice frequent user group with 31.03%. From this research, the authors propose a model that incorporates the habits, social factors and facilitating conditions in an Executive Information Systems.
基金Project(11271121)supported by the National Natural Science Foundation of ChinaProject(11JJ2002)supported by the Natural Science Foundation of Hunan Province,China+1 种基金Project(11K038)supported by Key Laboratory of Computational and Stochastic Mathematics of Ministry of Education of ChinaProject(2013GK3130)supported by the Scientific and Technological Plan of Hunan Province,China
文摘The electronic structures,chemical bonding,elastic and optical properties of the novel hP24 phase WB3 were investigated by using density-functional theory(DFT) within generalized gradient approximation(GGA).The calculated energy band structures show that the hP24 phase WB3 is metallic material.The density of state(DOS) and the partial density of state(PDOS) calculations show that the DOS near the Fermi level is mainly from the W 5d and B 2p states.Population analysis suggests that the chemical bonding in hP24-WB3 has predominantly covalent characteristics with mixed covalent-ionic characteristics.Basic physical properties,such as lattice constant,bulk modulus,shear modulus and elastic constants Cij were calculated.The elastic modulus E and Poisson ratio υ were also predicted.The results show that hP24-WB3 phase is mechanically stable and behaves in a brittle manner.Detailed analysis of all optical functions reveals that WB3 is a better dielectric material,and reflectivity spectra show that WB3 can be promised as good coating material in the energy regions of 8.5-11.4 eV and 14.5-15.5 eV.
文摘Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional theory calculation at wB97XD/6-31G（d） level. Strong interaction between porphyrin and heterofullerene moiety was predicted for these complexes based on geometry and electronic structure analysis. Especially, pseudobonding interaction occurring between the B atom of fullerene and the N atom of porphyrin was predicted to occur in C59B-ZnP complex, but be broken in C59B-ZnP complex. Time-dependent density functional theory calculation manifests the redshift of electron absorption for ZnP upon the interaction with heterofullerene.
