The distortion of an one dimensional transition-metal compound [Pd(cn)_2Pd(en)_2X_2]_n4+(X=Cl, Br, I) was studied by ab initio and EHT method. It was found that the degree of distortion was decided by the energy reduce of occupied orbit, interaction between metal nuclear and interaction among electrons. Base on it, the change rules of distortion and mixed-valence of [Pd(en)_2Pd(en)_2X_2]_n(4+)(M=Pt, Pd, Ni; X=Cl, Br, I) were explained reasonably. And it was shown that the δe of Pd in the complex varies linear with the deflection of d.

 A method of calculation of the amount of pyrene absorbed from the fluorescence emission spectrum has been developed. By this method the solubilization of pyrene from H2O/DMF solvent mixture to the crew-cut micelles of polystyrene-b-polyacrylic acid diblock copolymer has been investigated. The results showed that the solubilization of pyrene depends strongly upon water content in the solvent mixture. The amount 0f pyrene absorbed was enhanced with increasing the water content. The absorption isotherms were calculated and discussed by combination of the formula developed and the partition coefficient Kv. The theoretical treatment suggested an approach to calculate Kv directly from the intensity values measured experimentally.

 Conformations and hyperfine structures of the dimethylamino radical (CH_3)_2N and its protonated cation radical (CH3)2NH+ were studied at the UB3LYP/6-31G(d p) level, and isotropic hyperfine coupling constants on the α-proton, β-proton, and nitrogen nucleus (A(Hα), A(Hβ) and A(N)) of the two radicals were calculated using two DFT (UB3LYP and UB3PW91) methods and ab initio UHF and UMP2 (FULL) methods. The results of calculation indicate that the barriers to methyl group rotation in the two radicals are very low, being 0.46 and 2. 6 kJ•mol-1 for (CH3)2NH+ and (CH3)2N, respectively. The A (Hα), A(Hβ) and A(N) values in the two radicals are predicted by the UB3LYP/6-31G(d, p) and UB3PW91/6-31G(d, p) calculations in excellent agreement with experimental ones, and the UMP2 (FULL) /6-31G (d, p ) values are in quite od agreement with the experimental values.

The potential intermediates of a series of electrophilic agents reacting with ethene have been computed with PM3 semiempirical method. The results show that the energy of the bridged structure intermediates is lower than that of the open structure intermediates as the central atom of electrophilic agents is the third, fourth or fifth periodic element, but higher as the central atom is the first or second periodic element. Thereby, the electrophilic agents with third, fourth or fifth periodic element as central atoms should give stereospecific and non-regionspecific products and those with first or second periodic element as central atoms should give non-stereospecific and regionspecific Products. It is well an accordance with experimental results. Meanwhile, the model of d-π and s-p-π coordination bond has been put forward to try to explain the molecular mechanism.

The mixed oxide La2CuO4 was synthesized by four different methods and characterized with XRD, BET, TEM and low angle XRD. The effect of the synthetic method on the crystal structure, crystal size, surface area and catalytic activity to NO-CO reaction were studied. The results showed that the samples derived from different methods exhibited different activity to NO-CO reaction, the reason may be that the concentration and type of oxygen defect were different when the synthetic methods were different.

 Phthalocyanies bearing one crown-ether void can form complex with electron acceptors which contain alkai metal ions. The electron transfer reactions could be accelerated by the formation of the complex and the fluorescence of phthalocyanine was quenched significantly in this system. No fluorescence quenching of phthalocyanines without crown-ether substituted was observed under the same conditions. The steady constants of the complex can be calculated by non-linear least square fit method.

 The thermal behavior of SiO2-PEG/SiO2 xerogels was analyzed by using a temperature-programmed thermogravimertric method. The results showed the PEG in the xerogel had different thermal stability when the SiO2-PEG xerogel being heated under different atmosphere, and therefore influenced the textural properties. The apparent activation energy in different temperature stages was obtained from the DTG curves in N2. It indicated that the dehydroxyl reaction of SiO2 xerogel was kinetic-controlled, but, under ne the transition from kinetic-controll to diffusion-controll of the surface hydroxyl gradually with increasing temperature.

Water/TX-100/Hexanol/Octane reverse microemulsion system is studied by Microcalorimeter and FT-IR methods. The formation process of reverse microemulsions is an exothermic process and is a two step reaction. The first step is that hydrogen-bonds are formed between ether oxygen bonds of TX-100 monomers and water molecules, the second step is hydrogen-bond formation between ether oxygen bonds which are buried in aggregates and water molecules. Three types of water: bind water, trapped water, free water exist in this reverse microemulsion. This result is also proven by FT-IR. The stretch vibration peaks of hydroxyl of water are treated by curve-fitting method from 3035 cm-1 to 3700cm-1. The O-H stretch vibration frequency of trapped water, bind water and free water are 3550±20cm-1, 3400±20cm-1, 3220±20cm-1 respectively. Alkyl ether is prior to phenyl ether in acting with water because their polarity is different. Enthalpy contribution is the main driving force in the spontaneous formation...更多 of this reverse microemulsion. 

After cleaved in UHV, the dynamic band bending of GaAs(110) surface was investigated using in situ XPS measurement. It was found that the Fermi level of heavy doped n-GaAs and p-GaAs shifted to the midgap 0. 4 eV and 0. 3 eV, respectively. Fermi level difference of 1. 3eV between heavy doped n-GaAs and p-GaAs was revealed. In fact, the theoretical band gap of GaAs is 1. 42 eV, which suggests that our experimental results should be believable. Based on the experimental results, it was concluded that the surface band bending was caused neither by intrinsic surface states in GaAs, the residual gas in UHV, nor the X-ray radiation. The band bending should be caused mainly by the surface defects induced during the cleavage and more probably during lattice relaxation.

59Co solid static NMR has demontrated that the hydrogen bonding interaction plays an important role in the supramolecular complexes formed by the [Co (CN)6]3- and protonated polyammonium macrocycles. The 59Co chemical shift spans Ω in the supramolecular complexes containing hydrogen boning interaction are considerably larger than that in K3[Co(CN)6] which bears the electronic static interaction only. Hydrogen bonding interaction changes the symmetry, of [Co(CN)6]3- in the supramolecules leading to the split of the triplex degenerate state 1T1g and the extent of the split reveals the extent of the hydrogen bonding. Accordingly, the changes of the aquation quantum yields in the supramolecules are alternatively rationalized.

In this paper, polycrystalline powders of LaFeO3 have been prepared by the decomposation of mixed nitrates with and without various complexing agents respectively. The Phase changes at different temperatures have been investigated by XRD, TG, DTA and IR. The effects of adding complexing agent, citric acid, HAC and EDTA, on the formation of single phase LaFeO3 have been discussed. The formation of single phase perovskite-type LaFeO3 are favoured by adding various complexing agents. The favourable order for the formations of LaFeO3 is that citric acid＞HAC≈EDTA.

The effects of glucose and sucrose on the hydrated DHPE phase transitions have been studied by using differential scanning calorimetry. The experimental results demonstrated that the Lβ→Lα Phase transition temperature increased linearly with increasing the concentration c of sugars. With glucose, there is a relationship T=344. 37 +0.916 c(correlation coefficient r=0. 994; with sucrose, T=344.39+1.841c(r=0.9996). The ability of sucrose to decrease the Lα→HⅡ phase transition temperature was far stronger than that of glucose. In general, both glucose and sucrose could increase the cooperativity of Phase transition of hydrated DHPE, in addition to influence the phase transition enthalpies of hydrated DHPE. For the system of hydrated DHPE, both glucose and sucrose are kosmotropes, and they exert Hofmeister effect to influence the Phase transitions of hydrated DHPE. In comparison with glucose, sucrose should be quite a hopeful cryoprotectant in preservation of phospholipid bilayers structure.

Ketocoumarin dye 3-acetyl-7-diethylaminecoumrin was synthesized and charaterized. The spectra and photophysics behavior were studied in different aprotic solvents. Results showed that the fluorescence quantum yield had a maximum and the ratio of non-radiative transition rate to radiative transition rate had a minimum with the increasing of the solvent polarity. Also, the fluorescence of the dye can be quenched by triethylamine and the change is in accordance with the Stern-Volmer formula. These phenomenon was discussed preliminarily.

The CO oxidation reaction on DLA fractal surface has been studied in detail by Monte Carlo method. It was found that (1) when only adsorption and surface reaction were considered the O atoms and CO molecules on surface would self-organize after a reation period, which greatly decreased the touching chance among different reactant molecules and consequently decreased the reaction rate. Furthermore, O atoms tended to be adsorbed at the center or the inner area of DLA surface while CO molecules could exist only at the exterior; (2) the clusters of O atoms could be cut off by vacant active sites after the introduction of CO diffusion on surface, which would further give rise to accelerateion of the reaction rate; (3) when the reversible adsorption of CO was introduced O atoms and CO molecules could adsorb evenly on the whole DLA surface and then the reaction would be speeded up greatly, which suggested that for a od catalyst the adsorbing strength should be moderate.

The reaction dynamics of methylene radical CH2(X3B1) with N2O was investigated by Time-Resolved Fourier Transform Infrared Spectroscopy(TR-FTIRS). Pure CH2(X3B1) radicalwas produced via laser photolysis of ketene at 351 nm. Nascent viabrationally excited products CO, NO and HCN were observed. Some reaction pathways which may lead to these products were proposed and a possible reaction mechanism was outlined.

The performance of Cu/ZrO2 and Cu-La2O3/ZrO2 at different temperature was studied. The activity of both increased first and then decreased with the calcination temperature increased. This was due to the change of the copper dispersion and the interaction between copper and zirconia.

A series of Ce-Mo oxide catalysts with different Ce/Mo atomic ratio were prepared and applied to selective oxidation of toluene to benzaldehyde. The structures and properties of the surfaces of catalysts were characterized by XRD, TPR and DR-UVS. The natures of oxygen species on the surfaces of these samples were studied by using temperature programmed desorption-mass spectrography(TPD-MS). The results showed that the oxygen species of multiple adsorption existed on the sample surface. And in the range of desorption temperature<900℃, for the Ce-Mo samples, not only the desorption peaks of O- species on surfaces of samples be discoved, but also the O2- species appeared. As the content of Ce in Ce-Mo oxides was changed, the activation energy of oxygen desorption(Ed) also changed. The Ed value of sample 3 (Ce/Mo=1/1) is the lowest and its selectivity of benzaldehyde in toluene oxidation is the highest. Thus, a Parallel relation between the Ed value and the selectivity for benzaldehyde existed in these Ce-Mo oxides. 

The parallel complex reactions of H(2Sg) + CN(X2Σ+; V=0, 1; J=0)→HCN (X1 ∑+) and HNC(X1∑+ ) have been studied by using classical trajectory method. The results show that the two reactions all have not threshold energies. When the vibration state V= 0 for CN (X2∑+ ), there is not main superior product in HCN and HNC. When V=1 for CN(X2 ∑+),HCN is the more superior product. However, it has been discovered that Herschbach rule and the angular momentum rule can been all used in the reaction system, but their using ranges change with initially relative translational energies and vibration states for the reactant CN(X2 ∑+).