NH3-CH3OH system was studied by ab initio calculations at the Hartree-Fock level using the 6-31Gbasis set. Equilibrium geometries of both of its ionic (type I and II) and neutral clusters are obtained. Different disso...NH3-CH3OH system was studied by ab initio calculations at the Hartree-Fock level using the 6-31Gbasis set. Equilibrium geometries of both of its ionic (type I and II) and neutral clusters are obtained. Different dissociation channels are evaluated for I and II, respectively. The results suggest that when NH3-CH3OH is vertically ionized,CH3O + NH+ are the dominant products via a proton transfer reaction, and accompanying the dissociation of (NH3-CH3OH)+ver to NH3 + + CH3OH, intracluster charge transfer process takes place in the system.展开更多
The title compound ttris-(diisopropyldithiophosphato)tris-μ-disulfidoμ3,-sulfido-cvclo-trimolybdenumj (3Mo-Mo) [diisopropyldithiophosphate], [Mo3S7 (S2P(iprO)2)3] [S2P(iprO)2] (Mr=1365. 39) is an ionic species which...The title compound ttris-(diisopropyldithiophosphato)tris-μ-disulfidoμ3,-sulfido-cvclo-trimolybdenumj (3Mo-Mo) [diisopropyldithiophosphate], [Mo3S7 (S2P(iprO)2)3] [S2P(iprO)2] (Mr=1365. 39) is an ionic species which consists of a discretecluster cation [Mo3S7 (S2P (iprO)2)3] + (ipr = isopropyl) and an anion [S2P (iprO)2]-It was synthesized from the reaction of (NH4)2MoS4 with HS2P (iprO)2. Crystallo-graphic data for its crystal: space group for 7356 independent reflec-'tions with The structure analysis reveals that the cation contains a typical(Mo3 (μ3,-S) (μ-S2)3]+ cluster core in which three molybdenum atoms form an isoscelestriangle;the structure of the free diisopropyldithiophosphate anion [S2P (iprO)2]- isdifferent obviously from the coordinated one.展开更多
Mathematical modeling for nanofiltration of ionic liquids(ILs) solutions could assist to understand transfer mechanism and predict experimental values. In this work, modeling by solution-diffusion model for nanofiltra...Mathematical modeling for nanofiltration of ionic liquids(ILs) solutions could assist to understand transfer mechanism and predict experimental values. In this work, modeling by solution-diffusion model for nanofiltration of long-alkyl-chain ILs aqueous solutions was proposed. Molecular simulations were performed to validate the existence of ion cluster in long-alkyl-chain ILs aqueous solution. Based on the results of simulations, parameters used in the solution-diffusion model were modified, such as concentration of ILs and diameter of ion cluster.The modeling process was developed for three long-alkyl-chain ILs aqueous solutions with different concentrations(1-alkyl-3-methylimidazolium chloride: [C6 mim]Cl, [C8 mim]Cl, [C10 mim]Cl). The calculated values obtained from modified solution-diffusion model could well match the experimental values.展开更多
Two mononuclear metal-organic complexes, [Co（Hmpdc）2（H2O）4]·4H2O 1 and [Ni（Hfmpdc）2（H2O）4]·6H2O 2, were prepared from 2,6-dimethylpyridine-3,5-dicarboxylic acid （Hzmpdc） and 4-furyl-2,6-dimethylpyr...Two mononuclear metal-organic complexes, [Co（Hmpdc）2（H2O）4]·4H2O 1 and [Ni（Hfmpdc）2（H2O）4]·6H2O 2, were prepared from 2,6-dimethylpyridine-3,5-dicarboxylic acid （Hzmpdc） and 4-furyl-2,6-dimethylpyridine-3,5-dicarboxylic acid （H2fmpdc） with M（NO3）2 salts, respectively, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent measurement. Complex 1 crystallizes in triclinic, space group P1 with a = 7.634（5）, b = 8.695（5）, c = 10.757（6）A, α = 69.647（7）, β = 69.957（8）, γ = 83.733（7）°, V = 628.9（7）A^3, Dc = 1. 561 g/cm^3,μ（MoKa） = 0.763 mm^-1, F（000） = 309, Z = 1, the final R = 0.0553 and wR = 0.1469 for 1909 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Complex 2 crystallizes in monoclinic, space group P21/n with a = 9.5934（16）, b = 12.422（2）, c = 14.826（3） A, β = 105.201（2）°, V = 1705.0（5）A3, Dc = 1. 479 g/cm^3,μ（MoKa） = 0.655 mm^-1, F（000） = 796, Z = 2, the final R= 0.0351 and wR = 0.0889 for 2387 obsevved reflections （Ⅰ 〉 2σ（Ⅰ））. In the crystal structures of 1 and 2, diverse supramolecular motifs from 1-D chains/ladders to 3-D networks are constructed from corresponding distinct [M^Ⅱ（H2O）8] ion clusters as the second building units, respectively. The solid state compounds of 1 and 2 show similar photoluminescent spectra with emission maximum at ca.展开更多
Effects of shear rates on average cluster sizes (ACSs) and cluster size distributions (CSDs) in uni- and bi-systems of partly charged superfine nickel particles were investigated by Brownian dynamics, and clustering p...Effects of shear rates on average cluster sizes (ACSs) and cluster size distributions (CSDs) in uni- and bi-systems of partly charged superfine nickel particles were investigated by Brownian dynamics, and clustering properties in these systems were compared with those in non-polar systems. The results show that the ACSs in bi-polar systems are larger than those in the non-polar systems. In uni-polar systems the behavior of clustering property differs: at the lower ionic concentration (10%), repulsive force is not strong enough to break clusters, but may greatly weaken them. The clusters are eventually cracked into smaller ones only when concentration of uni-polar charged particles is large enough. In this work, the ionic concentration is 20%. The relationship between ACS and shear rates follows power law in a exponent range of 0.176-0.276. This range is in a good agreement with the range of experimental data, but it is biased towards the lower limit slightly.展开更多
In this paper, we studied the process of dissociation unimolecular of the evaporation of H+2n+1 hydrogen clusters according to size, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constants k(E) were ...In this paper, we studied the process of dissociation unimolecular of the evaporation of H+2n+1 hydrogen clusters according to size, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constants k(E) were determined with the use of statistical theory of unimolecular reactions using various approximations. In our work, we used the products frequencies instead of transitions frequencies in the calculation of unimolecular dissociation rates obtained by three models RRKM. The agreement between the experimental cross section ratio and calculated rate ratio with direct count approximation seems to be reasonable.展开更多
New typical ionic clusters with complex anions could be formed directly from the KNO 3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/...New typical ionic clusters with complex anions could be formed directly from the KNO 3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/z), which corresponded to the molecule weight of KNO 3 being 101 in the full mass spectrometry, of the positive ion and the negative ion. The general formula of the ionic clusters belonged to K+(KNO 3) n and NO- 3(KNO 3) m.展开更多
文摘NH3-CH3OH system was studied by ab initio calculations at the Hartree-Fock level using the 6-31Gbasis set. Equilibrium geometries of both of its ionic (type I and II) and neutral clusters are obtained. Different dissociation channels are evaluated for I and II, respectively. The results suggest that when NH3-CH3OH is vertically ionized,CH3O + NH+ are the dominant products via a proton transfer reaction, and accompanying the dissociation of (NH3-CH3OH)+ver to NH3 + + CH3OH, intracluster charge transfer process takes place in the system.
文摘The title compound ttris-(diisopropyldithiophosphato)tris-μ-disulfidoμ3,-sulfido-cvclo-trimolybdenumj (3Mo-Mo) [diisopropyldithiophosphate], [Mo3S7 (S2P(iprO)2)3] [S2P(iprO)2] (Mr=1365. 39) is an ionic species which consists of a discretecluster cation [Mo3S7 (S2P (iprO)2)3] + (ipr = isopropyl) and an anion [S2P (iprO)2]-It was synthesized from the reaction of (NH4)2MoS4 with HS2P (iprO)2. Crystallo-graphic data for its crystal: space group for 7356 independent reflec-'tions with The structure analysis reveals that the cation contains a typical(Mo3 (μ3,-S) (μ-S2)3]+ cluster core in which three molybdenum atoms form an isoscelestriangle;the structure of the free diisopropyldithiophosphate anion [S2P (iprO)2]- isdifferent obviously from the coordinated one.
基金financially supported by National Key Research and Develop Program of China (2017YFA0206803)National Science Fund for Excellent Young Scholars (21722610)+2 种基金National Natural Science Foundation of China (21676277)Key Program of National Natural Science Foundation of China (91434203)CAS-SAFEA International PartnershipProgramforCreativeResearchTeams (20140491518)
文摘Mathematical modeling for nanofiltration of ionic liquids(ILs) solutions could assist to understand transfer mechanism and predict experimental values. In this work, modeling by solution-diffusion model for nanofiltration of long-alkyl-chain ILs aqueous solutions was proposed. Molecular simulations were performed to validate the existence of ion cluster in long-alkyl-chain ILs aqueous solution. Based on the results of simulations, parameters used in the solution-diffusion model were modified, such as concentration of ILs and diameter of ion cluster.The modeling process was developed for three long-alkyl-chain ILs aqueous solutions with different concentrations(1-alkyl-3-methylimidazolium chloride: [C6 mim]Cl, [C8 mim]Cl, [C10 mim]Cl). The calculated values obtained from modified solution-diffusion model could well match the experimental values.
基金supported by the NNSFC (No. 20701041)the Key Project of Chinese Ministry of Education (No. 208116)+1 种基金the Natural Science Foundation of CQ CSTC (No. 2007BB5228)the Scientific and Technological Project of CQEC (No. KJ080829).
文摘Two mononuclear metal-organic complexes, [Co（Hmpdc）2（H2O）4]·4H2O 1 and [Ni（Hfmpdc）2（H2O）4]·6H2O 2, were prepared from 2,6-dimethylpyridine-3,5-dicarboxylic acid （Hzmpdc） and 4-furyl-2,6-dimethylpyridine-3,5-dicarboxylic acid （H2fmpdc） with M（NO3）2 salts, respectively, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent measurement. Complex 1 crystallizes in triclinic, space group P1 with a = 7.634（5）, b = 8.695（5）, c = 10.757（6）A, α = 69.647（7）, β = 69.957（8）, γ = 83.733（7）°, V = 628.9（7）A^3, Dc = 1. 561 g/cm^3,μ（MoKa） = 0.763 mm^-1, F（000） = 309, Z = 1, the final R = 0.0553 and wR = 0.1469 for 1909 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Complex 2 crystallizes in monoclinic, space group P21/n with a = 9.5934（16）, b = 12.422（2）, c = 14.826（3） A, β = 105.201（2）°, V = 1705.0（5）A3, Dc = 1. 479 g/cm^3,μ（MoKa） = 0.655 mm^-1, F（000） = 796, Z = 2, the final R= 0.0351 and wR = 0.0889 for 2387 obsevved reflections （Ⅰ 〉 2σ（Ⅰ））. In the crystal structures of 1 and 2, diverse supramolecular motifs from 1-D chains/ladders to 3-D networks are constructed from corresponding distinct [M^Ⅱ（H2O）8] ion clusters as the second building units, respectively. The solid state compounds of 1 and 2 show similar photoluminescent spectra with emission maximum at ca.
基金Projects(50474037, 50874087) supported by the National Natural Science Foundation of ChinaProject (BK2006078) supported by the Natural Scientific Funds of Jiangsu Province,China
文摘Effects of shear rates on average cluster sizes (ACSs) and cluster size distributions (CSDs) in uni- and bi-systems of partly charged superfine nickel particles were investigated by Brownian dynamics, and clustering properties in these systems were compared with those in non-polar systems. The results show that the ACSs in bi-polar systems are larger than those in the non-polar systems. In uni-polar systems the behavior of clustering property differs: at the lower ionic concentration (10%), repulsive force is not strong enough to break clusters, but may greatly weaken them. The clusters are eventually cracked into smaller ones only when concentration of uni-polar charged particles is large enough. In this work, the ionic concentration is 20%. The relationship between ACS and shear rates follows power law in a exponent range of 0.176-0.276. This range is in a good agreement with the range of experimental data, but it is biased towards the lower limit slightly.
文摘In this paper, we studied the process of dissociation unimolecular of the evaporation of H+2n+1 hydrogen clusters according to size, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constants k(E) were determined with the use of statistical theory of unimolecular reactions using various approximations. In our work, we used the products frequencies instead of transitions frequencies in the calculation of unimolecular dissociation rates obtained by three models RRKM. The agreement between the experimental cross section ratio and calculated rate ratio with direct count approximation seems to be reasonable.
文摘New typical ionic clusters with complex anions could be formed directly from the KNO 3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/z), which corresponded to the molecule weight of KNO 3 being 101 in the full mass spectrometry, of the positive ion and the negative ion. The general formula of the ionic clusters belonged to K+(KNO 3) n and NO- 3(KNO 3) m.
