UHF-SCF-AM1 MO calculations were performed for two kinds of pyrolysis reactions of seven nitro derivatives of methylbenzene(homolysis reactions by the rupture of bond C-NO_2 into radicals and isomerization reactions ...UHF-SCF-AM1 MO calculations were performed for two kinds of pyrolysis reactions of seven nitro derivatives of methylbenzene(homolysis reactions by the rupture of bond C-NO_2 into radicals and isomerization reactions in the way of methyl H transferring to the ortho nitro O atom). The molecular geometries of the reactants, the transition states and the products of the fourteen reactions were fully optimized. The activation energies for these two kinds of reactions have been obtained. The results indicate that this category of compounds is more easily pyrolyzed by being initiated via isomerization reactions. A parallel relationship exists between the activation energy of the isomerization reactions and the impact sensitivity of the seven titled compounds.展开更多
Molecular dipole moments computed at the levels of HF/STO-3G, HF/6-31G(d, p), HF/6-311+G(2d, 2p), MP2/6-31G(d, p) and MP2/6-311+G(2d, 2p) have been investigated. HF/6-311+G(2d, 2p) was found to be the relatively good ...Molecular dipole moments computed at the levels of HF/STO-3G, HF/6-31G(d, p), HF/6-311+G(2d, 2p), MP2/6-31G(d, p) and MP2/6-311+G(2d, 2p) have been investigated. HF/6-311+G(2d, 2p) was found to be the relatively good choice to compute MKS charges for reproducing the experimental values of molecular dipole moments. Root mean square deviation of computed dipole moments for 21 small polar molecules is about 0.1969 D.展开更多
Mulliken, NPA, MK and CHelpG population analyses have been accomplished at the level of MP2/6-31G（d,p） for the title system. The variations of four kinds of charges on NH3 with intermolecular distance infer that ele...Mulliken, NPA, MK and CHelpG population analyses have been accomplished at the level of MP2/6-31G（d,p） for the title system. The variations of four kinds of charges on NH3 with intermolecular distance infer that electron transfers from NH3 to H2O. MK and CHelpG population analyses indicate more electron transfer than Mulliken and NPA ones. The atomic charges resulted from MK and CHelpG schemes infer that electron transfers from N in NH3 to H in H2O, which confirms that this bimolecular complex possesses linear structure as H3N…HOH.展开更多
Two sets of widely used parameters can describe the molecular permeation through a nanochannel.One is permeation rate j and its diffusion Dn,and the other is flow and net flux.We establish a relationship between the t...Two sets of widely used parameters can describe the molecular permeation through a nanochannel.One is permeation rate j and its diffusion Dn,and the other is flow and net flux.We establish a relationship between the two sets for a single-file nenochannel,as well as its dependence on the temperature and pressure difference between the two ends of a single-file channel,based on the Brownian motion theories and verified with molecular dynamics simulations for the water diffusion in a transmembrane (6,6) armchair carbon nanotube.Simulation results are in excellent agreement with our predictions.展开更多
文摘UHF-SCF-AM1 MO calculations were performed for two kinds of pyrolysis reactions of seven nitro derivatives of methylbenzene(homolysis reactions by the rupture of bond C-NO_2 into radicals and isomerization reactions in the way of methyl H transferring to the ortho nitro O atom). The molecular geometries of the reactants, the transition states and the products of the fourteen reactions were fully optimized. The activation energies for these two kinds of reactions have been obtained. The results indicate that this category of compounds is more easily pyrolyzed by being initiated via isomerization reactions. A parallel relationship exists between the activation energy of the isomerization reactions and the impact sensitivity of the seven titled compounds.
基金The project was supported by the National Science Foundation (29773021) Provincial Educational Foundation of Jiangsu (98KJB150001).
文摘Molecular dipole moments computed at the levels of HF/STO-3G, HF/6-31G(d, p), HF/6-311+G(2d, 2p), MP2/6-31G(d, p) and MP2/6-311+G(2d, 2p) have been investigated. HF/6-311+G(2d, 2p) was found to be the relatively good choice to compute MKS charges for reproducing the experimental values of molecular dipole moments. Root mean square deviation of computed dipole moments for 21 small polar molecules is about 0.1969 D.
基金the National Science Foundation (29773021) and Provisional Educational Foundation of Jiangsu (98KJB150001).
文摘Mulliken, NPA, MK and CHelpG population analyses have been accomplished at the level of MP2/6-31G（d,p） for the title system. The variations of four kinds of charges on NH3 with intermolecular distance infer that electron transfers from NH3 to H2O. MK and CHelpG population analyses indicate more electron transfer than Mulliken and NPA ones. The atomic charges resulted from MK and CHelpG schemes infer that electron transfers from N in NH3 to H in H2O, which confirms that this bimolecular complex possesses linear structure as H3N…HOH.
基金Supported by the National Natural Science Foundation of China under Grant No 21173154the Pre-research Foundation of National Natural Science from Soochow Univerisity(No Q310904210).
文摘Two sets of widely used parameters can describe the molecular permeation through a nanochannel.One is permeation rate j and its diffusion Dn,and the other is flow and net flux.We establish a relationship between the two sets for a single-file nenochannel,as well as its dependence on the temperature and pressure difference between the two ends of a single-file channel,based on the Brownian motion theories and verified with molecular dynamics simulations for the water diffusion in a transmembrane (6,6) armchair carbon nanotube.Simulation results are in excellent agreement with our predictions.
