The role of the intersection between two potential energy surfaces has been more generally emphasizing on than before.In the present system,the intersections between S1,T1 and S0 surfaces were optimized with the state-averaged CAS(8,7)/6-31G method.The comparison of their optimized structures demonstrates that the intersection points of S1/S0 and S1/T1 locate in the same region,referred to as S1/T1/S0 point.The existence of S1/T1/S0 point and its high possibility of radiationless transition via intersystem crossing or internal conversion,would make the system have the most efficient funnel to generate the ground-and triplet-state products,which is consistent with the experimental facts.

Monomers of methacrylate with various [[pi]][/[pi]]-conjugated were designed and prepared in our laboratory.The monomer with suitable end-group was successfully assembled with nano-scale inorganic particles to form an orderly-aligned structure than showed special optical properties,both absorption and emission band were much red-shifted compared with the monomer.A new type of organic/inorganic hybrid materials was obtained by in situ polymerization of the assembly.The hybid materials could also show special potical properties as the assembly.This might poen a new route to tune the emission color.

In addition to our previous work of G2(ful) in Ref.[8],we proposed a further core electronic correlation modifieation at MP2/6-31G(d) level to G2(QCI),namely G2(QCI/ful),and that at MP2/6-311G(d,p) level to G2 and G2(QCI) theories,namely G2(fu2) and G2(QCI/fu2).The latter would need no additional calculation if the geometry is optimized at MP2(full)/6-311G(d,p) level/The modification energies,ΔE(fu2),were calculated via eq. ΔE(ful)=E[MP2](full)/6-31G(d)]-E[MP2(FC)/6-31G(d)] ΔE(fu2)=E[MP2](fu2)/6-311G(d,p)]-E[MP2(FC)/6-311G(d,p)] G2 and G2(QCI) theories were modified via eq. E[G2(fu2)]=E(G2)=ΔE(fu2)-HLC(G2)=HLC[G2(fu2)] E[G2(QCI/ful)]=E[G2(QCI)]+ΔE(ful)-HLC[G2(QCI)]+HLC[G2(QCI/ful)] E[G2(QCI/fu2)]=E[G2(QCI)]+ΔE(fu2)-HLC[G2(QCI)]+HLC[G2(QCI/fu2)] where, HLC[G2(fu2)]=-0.19nα-4.32nβ HLC[G2(QCI/ful)]=-0.19nα-4.77nβ HLC[G2(QCI/fu2)]=-0.19nα-4.65nβ It has been shown that the empirical High-Level-Correction(HLC) to either of the original G2 or G2(QCI) theory was reduced.G2(fu2) did not improve the over-all accuracy for the 125 G2-l test set reaction energies,however both G2(QCI/ful) and G2(QCI/fu2) did.The average absolute deviations (AAD) for the 125 reaction energse in the G2-l test set were reduced from 4.97 forG2(QCI) to 4.74 for G2(QCI/ful) and to 4.81kJ mol-1 for G2(QCI/fu2).The AAD was5.11 for G(fu2) compared with 5.09kJ mol-1 for G2.The reason for the larger AAD of G2(fu2) is probably due to that we did not use the better geometry of MP2(full)/6-311G(d,p) as presented in Ref.[11],and the 6-311G basis sets was somewhat unsatisfactory to describe both of the first-an secone-row atoms as had been criticized in Ref.[9].

The adsorption behaviors of xylenes in ITQ-l zeolite have been studied by using grand canonical Monte Carlo (GCMC) simulations.The simulated results indicate that the adsorption behavisrs of the studied sorbate molecules exhibit no obvious differences.Furthermore,the potential profile of xylenes migrating through the 10-MR windows interconnected cages have been determined,and the obtained results suggest that near 10-MR windows the potential barrier of o-xylene is significantly larger than that of m-xylene,which should block the diffusion of o-xylene into the interior of the zeolite,The theoretical calculations and experimental results show that m-xylene canmigrate through 10-MR windows systems interconnected 12-MR supercages and achieve the adsorption equilibria easily,while o-xylene can not overcome some potential barriers along 12-MR aupercages and arrive the iterior of the zeolite.

Theoretical study on PuOn+(n=1,2,3) using density function theory shows that PuO+ and PuO2+ are stable and PuO3+ unstable.Electronic states are Χ6Σ-(PuO+)、Χ5Σ-(PuO2+)、9Σ-(PuO2+) and 7Σ-(PuO2+),and their force constants and spectroscopin data have been obtained.

Ab initio calculations with RHF/6-31G,MP2/6-31G and MP2/6-31G have been applied to study the isomerization of 3-hydroxy-2-pyridine imine.The results obtained show that this isomerization proceeds via a four-center cyclic transition state(TS1) in the gas-phase,and via a six-center cyclic transition state (TS2) in water.The activation energy of the equation(2)through a six-center cyclic transtition state TS2 is the lowest(37.7kJ mol-1/RHF/6-31G(adjusted by Ev=0),27.0kJ mol-1/MP2/6-31G(adjusted by Ev=0)and 58.6kJ mol-1/MP2/6-31G),3-hydroxy-2-pyridine imine may have potential anticancer activity.

WO3/TiO2 samples were prepared by sol-gel process and characterized by means of XRD、LRS、TEM、DRS、BET、XPS.It has been shown that the mean crystal diameter and mean particle diameter of WO3/TiO2 samples decreased while the percent of anatase and specific surface area increased owing to the doping of WO3.New LRS peaks presented at 797,967 and 969cm-1,respectively,when the concentration of doped WO3 was 2%,5%and 8%.The reflectance percentate of WO3/TiO2 samples was less than that of pure TiO2 in the range of 380-460nm.The XPS fitting analyses showed that there were W6+、W5+、W4+ and Ti4+、Ti3+ in the lattice of WO3/TiO2.Being a model reaction,the photo-catalytic degradation of methylene blue was investigated in TiO2 and WO3/TiO2 nanopowder suspension irradiated by high-pressure mercury lamp.As a result,the addition of WO3 to TiO2 greatly enhanced its photo-catalytic behavior,and the optimum concentration of WO3 in TiO2 was 2%(molar percent).Moreover,the relationship between photo-activity and the physical and chemical properties of the samples have been discussed.

G3(QCI) model chemistry,which eliminates the uncertainties of basis sets and theoretical methods extrapolation approximations,is defined via eq.: E0[G3(QCI)]=E[QCISD(T,FC)/G3large]＋Δ E(full)＋ E(SO)＋ E(ZPE)＋ E(HLC) where the electronic energy E[QCISD(T,FC)/G3large] is directly calculated at QCISD(T,FC)/G3large level,the core electron correlation energyΔ E(full) is calculated at MP2/6-31G(d) (denoted as fu1) or MP2/6-311G(d,p) (denoted as fu2) level and the spin-orbit coupling E(SO) for atomic species is from the experiments as what has been done in the G3[2] theory.Four varieties of G2(QCI) model chemistry theoretical procedure,namely G3(qCI/fu1),G3(qCI/fu2),G3(QCI/fu1)//B3PW91;G3(QCI/fu2)//B3PW91,are proposed and tested with the G2-1 test set.The E(HLC)'s have been defined and optimized in the same manner as in G2 theory,which are -3.024na-5.397nβ on molecules and -2.085na-5.636nβ on atomic species for G3(QCI/fi1),-3.085na-5.478nβ on molecules and -1.885na-5.466nβ on atomic species for G3(QCI/fu2),-2.495na-5.478nβ on molecules and -1.70na-5.584nβ on atomic species for G3(QCI/ful)//B3PW91 and -2.670na-5.380nβ on molecules and -1.923na-5.465nβ on atomic species for G3(QCI/fu2)//B3PW91.The over-all accuracy is close to that of the G3 or G3/B3LYP method published in literature.The average absolute deviations on the G2-1 test set for these models are 4.37,4.39,4.06 and 4.02kJ mol-1,respectively,compared with 4.27 for G3 and 4.05 for G3//B3LYP on the same G2-1 test set.These results show further that the additivity or extrapolation approximation in the G3 theory is valid.However,the non-additive G3(QCI) procedures,which would be about four times of computer time consuming,in this work has been shown more reliable in the energy calculation of species at non-equiliberum geometry.Yhe maximum deveation of all of the four G3(QCI)'s occurs on the electronic affinity of the oxygen atom,e.g.-16.7 for G3(QCI/fu1) and -16.9kJ mol-1 for others compared with 17.6 for G3 and 18.4kJ mol-1 for G3//B3LYP on the electronic affinity of NH radical.In addition,this work suggests that the G3large basis sets for the first-row atoms are too small or the level of core-electronic energy calculations for the anions are too low since most of the larger errors are in the respective electronic affinities and this need to be further studied.

Ni-Mo alloy electrode, prepared by electrodeposition, were characterized for application to ethanol oxidation in 1 mol• L－ 1 KOH solution. Their electrochemical behavior was studied using cyclic voltammograms and quasi-steady-state current-potential curves. A mathematical model was developed to predict the behavior of ethanol oxidation on Ni-Mo alloy electrodes. The redox of Ni(OH)2/NiOOH couples in the alkaline solution is a preludial step for the ethanol electrooxidation, and the rate constants related to this reaction,k1 as well k－ 1,are functions of applied potential. Ethanol oxidation is carried out by a chemical reaction with rate constant kC1.The kinetic equations were derived and the kinetic parameters were obtained from a comparison of experimental results with kinetic equations. The rate constants of electrochemical reactions could be expressed as k1(E) =1.41× 107exp(0.5FE/RT)mmol• cm－ 2• s－ 1,k－ 1(E)=0.711 exp(0.5 FE/RT) mmol• cm－ 2• s－ 1,in which E was the applied potential vs SCE, and the chemical reaction rate constant, kC1,was 1.99× 10－ 4 cm• s－ 1.

The electrodeposition characteristics, structure and microhardness of Ni-W-P alloy have been studied by the methods of cyclic voltammetry, potentiostatic step and X-ray diffraction(XRD). The results showed that Ni-W-P alloy electrodeposit obtained from the solution containing ammonium citrate as complexing agent presented lower electrochemical activity compared with Ni-W alloy electrodeposit. Based upon the i～t curves of potentiostatic step, it was revealed that electrocrystallization of Ni-W-P alloy on glassy carbon electrode followed the mechanism of instantaneous nucleation and three dimensional growth with diffusion controll. The crystal nucleus number on the surface of electrode was raised by the increase of overpotential. XRD experimental results showed that the Ni-W-P alloy electrodeposits obtained were obviously of the amorphous structure, and the microhardness of the alloy was about 450 kg/mm2 at the stated plating solution and conditions.

The structure and catalytic properties of the ultrafine Co-Ce-O complex oxide particle catalysts for selective oxidation of 4-methylphenol(PMP) to 4-hydroxybenzaldehyde(PHB) have been studied by using TEM, XRD, XPS, BET surface area measurements and microreactor tests. It has been shown that the structure, composition and partical size of the ultrafine oxide particles exert great influences on the catalytic properties. Increasing cobalt content in the complex oxide. The catalytic activity for selective oxidation of PMP to PHB increases firstly and then decreases remarkably. It has been found that the higher activity of the ultrafine Co-Ce-O complex oxide particles catalysts for selective oxidation of PMP to PHB was not only correlated to their higher surface areas of the ultrafine particles but also correlated to the interaction between Co oxide and Ce oxide. Thermal treatments at higher temperatures result in sintering of the particles and destroy the interaction between Co oxide and Ce oxide, leading to remarkable decrease in the catalytic selective oxidation activity.

PS/TiO2 composite nanospheres were prepared in situ by seed emulsion polymerization, and the structure characterization was carried out by TEM、 UV-Vis、 FTIR、 DSC＆ TGA. The tribological behaviors of PS/TiO2 nanospheres as additives in paraffin oil were evaluated on a four-ball machine. Experimental results indicate that the PS/TiO2 composite nanospheres have a od anti-wear performance.

Measurements of surface tension, conductivity, aggregation behavior and solubilization of pyrene of chitosan aqueous solutions have been carried out. The results show that chitosan is surface-active, and can aggregate in single molecule, or critical aggregation number cac≈ 0. It is clear that chitosan is a cationic macromolecular surfactant with special structure and properties.

In this work, mixtures of HCHO-NO2-Ar were photolyzed under stationary conditions using a high-pressure Hg lamp atλ =300～ 340 nm and HCHO as a probe molecule. The HCO radicals were generated in the reaction system, and the kinetics of the reaction between HCO radicals and NO2 was investigated at room temperature in Ar gas at 5.7× 104 Pa pressure by FTIR spectroscopy. The main reaction products including CO, CO2, NO, HONO and H2O were detected. A small amount of N2O was found only at longer reaction times when NO2 consumption was complete. These product molecules were formed in consecutive reactions from several reaction channels. From the yields of CO and CO2,branching ratios were determined and their kinetic mechanism was discussed.

The heat of the thermal decomposition of monoclini c ammonium paratungstate, (NH4)10H2W12O42•4H2O, was measured in a HT-1000 microcalorimeter using three-step calorimetry and suitable thermochemical cycle. The standard enthalpy of the thermal decomposition reaction at 298.15 K and the standard enthalpy of formation at 298.15 K for monoclinic ammonium paratung-state were obtained to be (430.1± 10.2) kJ•mol－ 1 and－ (13 423.7±14.8) kJ•mol－ 1, respectively.

The standard transfer Gibbs energy(ΔtrGΘ ) of potassium tetraphenylborate (KBPh4) from water to water and 2-propanol solvent mixtures and from methanol to methanol and 2-propanol solvent mixtures within the whole concentration range of the mixed solvents are studied at 298.15 K. TheΔtrGΘ value of KBPh4 reaches an extreme value from water to water and 2-propanol solvent mixtures, while it increases monotonically with an increasing of 2-propanol content in methanol and 2-propanol solvent mixtures. This indicates the different interaction of KBPh4 with the two kind of solvent mixtures.