The critical _d vahues ( _ ) of the γ/(γ+σ).γ/(γ+μ) and γ/(γ+γ') phase boundaries in some ternar alloy phase diagrams at various temperatures are calculated by averaging the _d values of sererai selecte...The critical _d vahues ( _ ) of the γ/(γ+σ).γ/(γ+μ) and γ/(γ+γ') phase boundaries in some ternar alloy phase diagrams at various temperatures are calculated by averaging the _d values of sererai selected characteristic points at the phase boundaries.Approxmate equations for the temperature dependence of the critical _d of γ/(γ+σ).γ/(γ+μ) and γ/(γ+γ') phase boundaries are established.The accuracy of the analysis is discussed in detail. It is found for the first time that the average value of the bond order _ at the phase boundaries ts also approximatelr a constant and therefore a critical average bond order _ like - can be introduced for the analysts of phase stability展开更多
Ab initio molecular orbital calculations of doubly negative charged B16H162-(D2) and neutral B16H16(Td) have been done at the HF/6-31G level.They are predicted to be chemically and kinetically stable by vibrational an...Ab initio molecular orbital calculations of doubly negative charged B16H162-(D2) and neutral B16H16(Td) have been done at the HF/6-31G level.They are predicted to be chemically and kinetically stable by vibrational analyses on their respective energy hypersurface of the HF/6-31G level.The geometrical structure of the species B16H1622-(D2) was discussed.展开更多
The Ti-Supported MnO_2 electrode was modified by introducing SnO_2+RuO_2+MnO_2 as an intermediate layer into the Ti/MnO_2 interface. The anodic polarization curves were measured at various temperatures ranging from 30...The Ti-Supported MnO_2 electrode was modified by introducing SnO_2+RuO_2+MnO_2 as an intermediate layer into the Ti/MnO_2 interface. The anodic polarization curves were measured at various temperatures ranging from 30 to 80℃ and the activation energy for the oxygen evolution reaction was evaluated. The experimental activation energy increased linearly with increasing the overpotential. The activation energy at the equilibrium potential was linearly correlated with the difference between the crystal field stabilization energies of Mn^(4+) at initial state and Mn^(4+) at transition state. The electrocatalysis characteristics of the anode were discussed by means of the mechanism of the substitution reaction of the ligand(S_N1 and S_N2) and molecular orbital theory. The results show that the anode has better electrocatalystic characteristics.展开更多
The chemisorption properties of N^18O adsorption on TiO2(110) surface were investigated by experimental and theoretical methods. The results of temperature programmed desorption (TPD) indicated that the temperatures o...The chemisorption properties of N^18O adsorption on TiO2(110) surface were investigated by experimental and theoretical methods. The results of temperature programmed desorption (TPD) indicated that the temperatures of the three desorption peaks of the main N2 molecules were at (low) temperature of 230 K, 450 K, and (high) temperature of 980 K. This meant that N^18O decomposed and recombined during the process of N2 desorption after N^18O was exposed. Analysis of thestable combination and orbital theory calculation of the surface reaction of NO adsorption on the TiO2(110) cluster modelshowed that there was clear preference for the Ti-NO orientation.展开更多
A convenient synthesis and theoretical study of five CCK-functional dendrimers is described. The dendritic cores were linked with the CCK（Trp-Met-Asp（OBn）-PheNH2） fragment by forming amide bonds to give five targe...A convenient synthesis and theoretical study of five CCK-functional dendrimers is described. The dendritic cores were linked with the CCK（Trp-Met-Asp（OBn）-PheNH2） fragment by forming amide bonds to give five target molecules. The structures of CCK-functional dendrimers were characterized by NMR, MS spectrum and predicted using molecular mechanics and PM3 semi- empirical molecular orbital theory.展开更多
The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted add...The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.展开更多
Chlorophenols(CPs),as important contami-nants in groundwater,are toxic and difficult to biode-grade.Recentlynanoscalezero-valentironreceivedagreat deal of attention because of its excellent performance in treating rec...Chlorophenols(CPs),as important contami-nants in groundwater,are toxic and difficult to biode-grade.Recentlynanoscalezero-valentironreceivedagreat deal of attention because of its excellent performance in treating recalcitrant compounds.In this study,nanoscale zero-valent iron particles were prepared using chemical reduction,and the reductive transformations of three kinds of chlorinated phenols(2-CP,3-CP,and 4-CP)by nanoscale zero-valent iron under different conditions were investigated.The transformation process of the CPs was shown to be dechlorination first,then cleavage of the benzene ring.The removal efficiency of the CPs varied as follows:2-CP.3-CP.4-CP.The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit(E LUMO).With the increase in initial concentrations of CPs,removal efficiency decreased a little.But the quantities of CPs reduced increased evidently.Temperature had influence on not only the removal efficiency,but also the transformation pathway.At higher temperatures,dechlorination occurred prior to benzene ring cleavage.At lower temperatures,however,the oxidation product was formed more easily.展开更多
Structures, energies and vibrational frequencies have been calculated for hollow cage clusters N28, B4N24, B12N16, and B16N12 with Td symmetry using ab initio quantum mechanical methods at the RHF/3-21G level. Each sp...Structures, energies and vibrational frequencies have been calculated for hollow cage clusters N28, B4N24, B12N16, and B16N12 with Td symmetry using ab initio quantum mechanical methods at the RHF/3-21G level. Each species is predicted to be both chemically and kinetically stable. Skeletal polyhedrons of all considered boron nitride hollow cage clusters are constructed from 5- and 6-membered rings.展开更多
文摘The critical _d vahues ( _ ) of the γ/(γ+σ).γ/(γ+μ) and γ/(γ+γ') phase boundaries in some ternar alloy phase diagrams at various temperatures are calculated by averaging the _d values of sererai selected characteristic points at the phase boundaries.Approxmate equations for the temperature dependence of the critical _d of γ/(γ+σ).γ/(γ+μ) and γ/(γ+γ') phase boundaries are established.The accuracy of the analysis is discussed in detail. It is found for the first time that the average value of the bond order _ at the phase boundaries ts also approximatelr a constant and therefore a critical average bond order _ like - can be introduced for the analysts of phase stability
文摘Ab initio molecular orbital calculations of doubly negative charged B16H162-(D2) and neutral B16H16(Td) have been done at the HF/6-31G level.They are predicted to be chemically and kinetically stable by vibrational analyses on their respective energy hypersurface of the HF/6-31G level.The geometrical structure of the species B16H1622-(D2) was discussed.
基金Supported by the National Natural Science Foundation of China.
文摘The Ti-Supported MnO_2 electrode was modified by introducing SnO_2+RuO_2+MnO_2 as an intermediate layer into the Ti/MnO_2 interface. The anodic polarization curves were measured at various temperatures ranging from 30 to 80℃ and the activation energy for the oxygen evolution reaction was evaluated. The experimental activation energy increased linearly with increasing the overpotential. The activation energy at the equilibrium potential was linearly correlated with the difference between the crystal field stabilization energies of Mn^(4+) at initial state and Mn^(4+) at transition state. The electrocatalysis characteristics of the anode were discussed by means of the mechanism of the substitution reaction of the ligand(S_N1 and S_N2) and molecular orbital theory. The results show that the anode has better electrocatalystic characteristics.
文摘The chemisorption properties of N^18O adsorption on TiO2(110) surface were investigated by experimental and theoretical methods. The results of temperature programmed desorption (TPD) indicated that the temperatures of the three desorption peaks of the main N2 molecules were at (low) temperature of 230 K, 450 K, and (high) temperature of 980 K. This meant that N^18O decomposed and recombined during the process of N2 desorption after N^18O was exposed. Analysis of thestable combination and orbital theory calculation of the surface reaction of NO adsorption on the TiO2(110) cluster modelshowed that there was clear preference for the Ti-NO orientation.
文摘A convenient synthesis and theoretical study of five CCK-functional dendrimers is described. The dendritic cores were linked with the CCK（Trp-Met-Asp（OBn）-PheNH2） fragment by forming amide bonds to give five target molecules. The structures of CCK-functional dendrimers were characterized by NMR, MS spectrum and predicted using molecular mechanics and PM3 semi- empirical molecular orbital theory.
基金Ⅴ. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.20833008）.
文摘The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.50678089 and 50325824),which is greatly acknowledged.
文摘Chlorophenols(CPs),as important contami-nants in groundwater,are toxic and difficult to biode-grade.Recentlynanoscalezero-valentironreceivedagreat deal of attention because of its excellent performance in treating recalcitrant compounds.In this study,nanoscale zero-valent iron particles were prepared using chemical reduction,and the reductive transformations of three kinds of chlorinated phenols(2-CP,3-CP,and 4-CP)by nanoscale zero-valent iron under different conditions were investigated.The transformation process of the CPs was shown to be dechlorination first,then cleavage of the benzene ring.The removal efficiency of the CPs varied as follows:2-CP.3-CP.4-CP.The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit(E LUMO).With the increase in initial concentrations of CPs,removal efficiency decreased a little.But the quantities of CPs reduced increased evidently.Temperature had influence on not only the removal efficiency,but also the transformation pathway.At higher temperatures,dechlorination occurred prior to benzene ring cleavage.At lower temperatures,however,the oxidation product was formed more easily.
基金Project supported by the National Natural Science Foundation of China.
文摘Structures, energies and vibrational frequencies have been calculated for hollow cage clusters N28, B4N24, B12N16, and B16N12 with Td symmetry using ab initio quantum mechanical methods at the RHF/3-21G level. Each species is predicted to be both chemically and kinetically stable. Skeletal polyhedrons of all considered boron nitride hollow cage clusters are constructed from 5- and 6-membered rings.
