The reaction of vinyl radicals with oxygen was investigated by Time-Resolved Fourier Transform infrared emission spectroscopy. The radicals were produced by the pulsed laser photolysis of C_2H_3Br at 248 nm. Vibrationally excited products of H_2CO(v1), HCO(v3), CO_2(v3, v), CH_3(v3), C_2H_2(v3), HO_2(v1), C_2H_2O_2(v3+v11), CO(v) formed in the C2H3+O_2 reaction have been observed. Four elementary reaction channels have been verified.

Surplus function variational quantum Monte Carlo (SFVMC) approach for the electronic excited state has been established in this paper. It is demonstrated that if the initial wave functions of the excited state and ground state belong to the irreducible representation with different symmetry, SFVMC approach of excited state is identical to that of ground state, if they belong to the irreducible representation with identical symmetry, SFVMC approach of the ground state can also be applied to the excited state only the initial wave function of excited state requiring ortho nal adjustment. The detailed calculations of SFVMC approach of the excited state are also deduced in this paper. A complete set of SFVMC approach for the ground state and excited state has been establised in combination of the ground state's SFVMC approach which was deduced in our previous paper[1]. The energy values of X 3B_1, state, 1 1A_1 state, and 2 1A_1 state of CH_2 molecule have been calculated by this approach as an example. The calculation results (to see Table 1 ) show that the precision of SFVMC approach can achieve that of FCI approach by only iteration to the third order energy value for three states of CH_2 molecule. The correlation energy percentages of the fourth order energy and the fifth order energy are above 80% and 90% by SFVMC approach, respectively. This discloses that SFVMC approach is successful not only for the ground state but also for the excited state. 

The reaction mechanism of reaction O(3P) + CIONO_2→CIO + NO_3 and reaction O(3P) + CIONO_2 →O_2→CIONO has been studied with B3LYP/6-31G* method. The results show that the activation energy of the first reaction is 1. 79kJ•mol-1. There are two possible reaction pathways for the second reaction: O (3P) attacks two different oxygen atoms of CIONO_2. The activation energies are 90.56 and 96.60 kJ•mol-1 respectively. The first reaction is therefore the main reaction because of its low activation energy. And the two reaction pathways of the second reaction can occur simultaneously for their same order of magnitude of activation energies.

Molecular reaction dynamics for the collision Al(2P_u ) +H_2 (X 1 ∑_g+ , v=j=0)has been studied based on the analytical potential energy function of AlH_2(X2 A_1) by using Monte-Carlo quasi-classical trajectory approach. The results for the collision process indicate that the main channel is the exchange reaction Al (2P_u) + H_2 (X 1 ∑_g+, v=j=0)→AIH(X 1 X+, v', j' ) + H(2 S_g ) with product AlH and no complex compound AlH_2(X 2 A_1) was formed. The relation of reactive cross section σ_r, with relative kinetic energy E_t apparently shows that there is a threshold energy of 314KJ• mol-1. Because the mass of aluminium atom is much heavier than that of hydrogen atom, the product AlH distribution is along the direction of the forward scattering.

Molecular dynamics has been performed to study the diffusion behaviors of benzene molecules in pure siliceous MCM-22 analog: ITQ-1. The diffusion coefficients of benzene do not show obvious differences using rigid zeolite framework or flexible zeolite framework, which means the flexibility of the zeolite framework does not introduce remarkable effects to the simulation results. From the trajectories of molecular dynamics, it can be found that the diffusion and migration of benzene mainly occured in 12-MW cavities, while high activtion energy must be needed when one sorbate molecule migrating from one 12-MW cavity to another nerarby 12-MW cavity through the 10-MW windows. Moreover, the diffusion characteristics of the benzene molecules indicates that a pair of benzene molecules in S1 and S2 sites will produce relatively strong π－π stacking force and the motions between two benzenes near S1 and S2 sites will keep very synergistic status in order to make the system remaining in the state of optimal energy.

Study on the kinetics of oxidation of Ti-enriched slag (CaO-SiO_2-Al_2O_3-M -TiO_x-FeO_y system)was carried out by E. M. F. method and chemical analysis. The diffusion rate constants of oxygen within the molten slag were obtained which are 0.66×10-5 m•s-1 and 1.98×10-5 m• s-1 respectively. The experimental work showed that E. M. F. is a quick and convenient method.

A modified catalyst composed of heteropoly compound and α-Sb_2O_4 with oxygen spillover effect was used for the selective oxidation of t-butanol (isobutylene). Methacrylic acid (MAA) was the main product by one-step process. By optimizing the conditions of catalyst preparation and oxidation reaction, the yield of MAA is 50% and the total yield of MAA and methacrolein (MAL) is above 75%. The catalyst revealed a od potential application in industry. The physicochemical characterization of the catalysts (DTA, IR, and XRD) has been reported and the influence of preparation condition on catalytic activity has been examined in this paper.

High-level ab initio, QCISD (T) /6-311 + G(3 df, 2p), energy from the least accurate theoretical bond distance was calculated and compared with that from the experimental geometry on each of the thirty four diatomic molecules having a relative error (ropt. - rexp. ) / rexp. of theoretical bond length greater than 2%. These molecules were chosen from all of the sixty first- and second-row diatomic inorganic species collected in the 77th CRC Handbook of Chemistry and Physics involved in our previous comparison of systematic geometry optimizations. It was found, unexpectedly, that QCISD(T) /6-311 + G (3 df, 2p) calculations did not result in the lowest energy with the experimental bond distance in a few cases, which implies that QCISD(T)/6-311 + G(3df, 2p) method has some deficiencies in the point of view of "high-level ab initio". Most of the QCISD . (T) /6-311 + G(3 df, 2p) energy divergences between the two different geometries were less than 4. 2 kJ. mol-1 with six exceptions with BN,CN, CP, N_2, O_2 and SiN molecules and especially on CN radical, Which resulted in an error as large as 15.8 kJ• mol-1 at the MP2 (full) /6-311G(2 d, p) geometry. For CN, CP and SiN radicals, the energy errors were also from the poor geometry of MP2 optindzations. It was also found that the larger the basis sets used the poorer the geometries were for these three radicals at MP2 level. For the ground state of BN(3∏) radical, the experimental bond length 128. 1 pm maybe in doubt and has to be re-examined. For N_2 and O_2, MP2(full) gradient optimization at the basis sets of valence triple-ξ, 6-311G (d, p ), improved the geometries as well as the high-level QCISD(T) energies compared with what at the valence double-, 6-31G(d, p), basis sets.

At low concentration (0.4%), in the present of n-butanol, alkanes and brine, petroleum sulfonate (SPS) which has wide range of molecular weight, can form middle phase microemulsion. Using salinity, n-butanol scanning and interfacial tension, we investigated the influence of salinity, n-butanol and kind of alkane on the formation and characteristics of the middle Phase microemulsion of 0.4% SPS/ n-butanol/NaCl/alkane system at V_oil/ V_water=1: 4. Using mimic oil recovery, we investigated the influence of salinity on oil recovery efficiency. It showed in this study that the maximum oil recovery efficiency was connected with optimal salinity and optimal interfacial tension. The results are of particular importance to design slug formation.

The interaction of a group of new synthetic compounds, dioxycyclobutenedione- (1, 2 -cyclohexanedimine ) platinum (Ⅱ) (DCP ) and its stereoisomers, with calf thymus DNA was investigated by DSC and NMR methods. In the presence of three stereoisomers of the compounds, the melting temperatures of DNA are 350.45 (SS, trans-d-l-DCP), 349.65 (RS, cis-DCP) and 348.85(RR, trans-1-DCP) )K respectively, while the melting temperature of DNA is 351.05 K. Comparing the 13C NMR spectra of three stereoisomers of the compounds with and without DNA to that of squaric acid at pH = 7. 0 and room temperature, it can be obviously seen that square acid bases dropped out of the compound molecules as leaving group and t into the solutions as they bound to DNA. On the basis of the above experimental results, the binding strength and the model of the compounds with DNA have been discussed.

The lithiation behavior of a-Fe_2O_3, is investigated at ambient-temperature in LiOH solutions by methods of cyclic voltammetry, IR and tracking XRD and ICP analyses. The results reveal that lithiation can take place to a small extent in α-Fe_2O_3 and its electrochemically synthesized product is Fe_3O_4 but lithiation process is limited by the unavoidable extrusion of iron in alkaline solutions. It is suggested that Li+ intercalation promotes iron's extrusion from α-Fe_2O_3 and Fe_3O_4, and that a coordination effect occurs between lithiation and iron extrusion, which shortens the steps of cyclic curves and improves the capacity significantly. These results are compared with experiments, in which α-Fe_2O_3 electrodes cycled in KOH solutions are tested by CV, XRD and ICP.

A polymer film of hemin was obtained on a graphite carbon electrode by cyclic voltammetric method in aqueous solution. Cyclic voltammograms of the film electrode in 0.1 mol•L-1 NaOH exhibited two pairs of stable and reversible redox waves with peak formal potential at -730 mV and 530 mV respectively. For thicker films at faster potential scan rates, peak currents proportional to (scan rate)1/2 means charge transport is controlled by diffusion in the films. Protonated films have anionic exchange properties. The poly-hemin electrode shows od electrocatalytic reduction capacity for oxygen. After a long period reduction of oxygen, the electroactivity of film was diminished.

Surface modified nanostructured ZnO was prepared by means of ultrasonic induced reaction within microemulsion system consisting of surfactants such as PEG, Span 80 and cyclohaxane/H2O. The morphology, interaction between nano ZnO particles and surfactants, UV-absorption behaviors were characterized by TEM, IR and UV.

The microstructural characteristics of water/N, N-dibutyldecanamide/CCl4 system have been investigated by FT-IR spectroscopic technique. The broad peaks obtained for water OH have been resolved by Gaussian curve fitting, and the vibration characteristics, particularly the peak intensity and peak area corresponding to each peak, have been analyzed. The results suggest the formation of 1: 1 and 2:1 hydrogen bonded complexes, DBDEA. H2O and (DBDEA)2• H2O, respectively. There is no evidence for the multihydrate species.

The adsorption of CO_2 and NO on supported Pd catalysts has been studied by using TPD-MS method and the adsorbed surface species were discussed based on literatures. The amount and intensity of basic sites increase when promoter Li is added, whereas the amount of basic sites decreases when Ce is added. It is found that there are three kinds of basic sites with different intensity on the catalyst surface. On sample Pd/Al_2O_3 and Pd/Al_2O_3-Li_2O, large amount of CO desorption species is detected, this shows some CO_2 on the surface being decomposed. There is no such effect on the sample Pd/Al_2O_3-CeO_2. After analyzing the TPD profiles of NO adsorption on catalysts, it is found that both the NO desorption amount and the shapes of desorption peaks change remarkably when promoter Li or Ce is added. In the case of Li, the γ-peak (nitrate and nitrite species on surface) of NO desorption increases, the intermediate N_2O desorbs at higher temperature. In the case of Ce, the α-peak (species on the Brönstesd acidic sites ) of NO desorption decreases, and N_2O desorbs at lower temperature.

Photoionization and Photodissociation of epichlorohydrin are performed using a time-of-flight mass spectrometer(TOF-MS) with vacuum ultraviolet(VUV) photons from Hefei synchrotron radiation source. Photoionization mass spectrum and photoionization efficiency(PIE) curves of the fragment ions are measured. The appearance potentials of the fragment ions are obtained from their PIE curves. From these data, the formation enthalpies of some ions have been evaluated and their possible channels of dissociative photoionization have been discussed. The experimental results show that the mother ion of epichlorohydrin is unstable and the chlorine atom is easily lost to form ring C_3H_5O+ ion. Other fragment ions come from the dissociation of C_3H_5O+ ions.

Metallothionein, a class of low molecular weight, metal- and cysteine-rich Proteins, are postulated to play a central role in metal-related biological processes such as the detoxification of Cd2+and Pb2+. The thermal Properties of the interactions of rabbit liver Zn_7MT2 and apo-MT2 with Cd2+ and Pb2+ were studied using isothermal titration calorimeter. The same product Cd_7MT formed in the reactions of Cd2+ with Zn_7MT2 and apo-MT2, while the reactions of Ph2+ with Zn_7MT2 and apo-MT2 Produced two MT species Ph_7MT and Ph_7MT'. The thermodynamic parameters (△H、 △G、 △S, etc. ) for the reactions of MT with 1 mol metal ions were measured at 293.15 K, pH 4.70. All of these reactions are spontaneous, exothermic processes. The values of △G and K show that Cd2+ is more affinitive to MT than Ph2+. The equilibrium constants K of the replacement reactions of Zn_7MT2 by 1 mol Cd2+ and Pb2+ are 2. 7×105 and 1. 3×105 respectively, that means the concentrations of free Cd2+ and Pb2+ are depressed to about 1. 0×10-5 after the reactions with Zn_7MT2. These data can be used to evaluate quantitatively the ability of MT in Cd2+ and Pb2+ detoxificatio.