Hel photoelectron spectroscopic (PES) and quantum chemistry study on the dimeric compound of 2(5H) furanone

The HeI photoelectron (PE) spectra of both 2(5H) furanone and its trans-chair-dimenc-compound (t-c-DFN) are reported.The assignment of the PES bands is made on the basis of band shapes,the PES results of the molecules which have the similar atomic groups,and the restricted Hartree-Fock (RHF) calculations for the molecules studied.From the results of both PES experimental and theoretical calculations,it is proved that the ionization potential (IPs) of the HOMO for the dimenc-compound is lower than that of the HOMO for the monomer.And the total energy computed for the t-c-DFN is the lowest in the four possible configurations of dimeric-compounds of 2(5H) furanone Therefore the synthesis of t-c-DFN is also the easiest.     

THE HEI PHOTOELECTRON SPECTROSCOPIC STUDY OF MICROWAVE-DISCHARGED SPECIES OF METHYL IODIDE

The detection of the microwave-discharged species of methyliodide by HeI photoelectron spectroscopy(UPS)is reported for the firsttime.The UPS spectra of I_2 and HI molecules clearly appeared in thespectrum of microwave-discharged species of methyl iodide,The mechanismof the change of methyl iodide under microwave discharge wasproposed,The result provides the basis for understanding depletion ofthe ozone shell of the atomsphere by halogenated methane.     

异吲唑硝基取代衍生物的HEI2光电子能谱——-"轨道换向"现象的又一例证

The HeIα PES of indazole (1a), 3-bromoindazole (2a) and their isomeric nitro derivatives 1b-e and 2b-e have been recorded. It has been found that the lowest π^-^1 ionization energies (I1)^m, (I2)^m are moved towards higher energies under the influence of the nitro group, but that there is no significant dependence of the size of the shifts (ΔI1)^m, (ΔI2)^m on the position of the group. The result, which is at variance with the predications derived from a naive perturbation treatment based on the π orbitals of 1a, has been explained as being due to "orbital switching" in the substituted derivatives.     

SYNTHESIS AND CHARACTERIZATION OF POLY(STYRENE-co-4-VINYLPYRIDINE) NEODYMIUM COMPLEX

Poly(styrene-co-4-vinylpyridine)-neodymium complexes(NdCl_3·PS4VPY)with variouscontents of the functional group and neodymium have been prepared and characterized.Theinfrared and X-ray photoelectron spectra indicate that uncoordinated 4-vinylpyridine(4VPY)unitsremain in the NdCl_3·PS4VPY complexes.The catalytic behaviour of NdCl_3·PS4VPY was described briefly.     

~1H NMR INVESTIGATION OF THE BINDING OF METHYL-β-D-GALACTOSES WITH SIALIC ACID RESIDUES ON HEPATIC BINDING PROTEIN——THE EFFECT OF DIVALENT CALCIUM ION

The present study is a proton NMR investigation of the influence of Ca~(2+) on the interaction between the intact sialic acid residues on HBP (Hepatic Binding Protein) and methyl-β-D-galactoses. The proton NMR spectra of HBP and methyl-β-D-galactose mixing solution at different Ca~(2+) concentratiou have been measured. The analysis of the experimental results indicates that Ca~(2+) participates in the binding of sialic acid residues on HBP with methyl-β-D-galactoses and this enables the galactose molecules to, be in stable bound state. The proton NMR spectra of the samples containing EDTA have confirmed this conclusion.     

XPS STUDY ON THE DERIVATIVES OF N-β-PHENETHYL AMINE AND N-β-PHENETHYL GLYCINE

The X-ray photoelectron spectra of sixteen derivatives of N-β-phenethyl amine and N-β-phenethyl glycine have been studied. The effect of different structures on N_(1s) binding energy and that of their Pauling's atomic charge density on the nitrogen atoms are investigated. The experimental binding energy of N_(1s) is proportional to the calculated Pauling's atomic charge density. It shows that the phosphoryl group is the strongest nitrogen lone pair electron localizing group as compared with the corresponding sulfonyl and acyl derivatives. The XPS results agree with the data that there is no decarbonylation during the synthesis of N-dialkylphosphoryl-tetrahydro-3-benzazepin-l-one.     

Effects of Self—coiling of Organic Molecules on Intramolecular Exciplex Formation and Fluoresscence Quenching in DX—H2O Solvent System

Effects of self-coiling of organic molecules on intramolecular exciplex formation of compound I,in which the carbazole chromophore and terephthalic acid methylester acceptor group are linked by one (CH2)10 chain,and the decrease of the fluorescence intensities of compounds Ⅱ，Ⅲ，and Ⅳ,in which the carbazole chromophore and 3,5-dinitrobenzoate are connected by one aliphatic chain of (CH2)10 (Ⅱ），（CH2）12（Ⅲ）,or (CH2)4(Ⅳ）,have been studied in the dioxane (DX)-H2O binary system.The results show that self-coiling of organic molecules in DX-H2O facilitates intramolecular exciplex formation of I and induces the decrease of fluorescence intensities of Ⅱ,bacause of the proximity effect brought about by selfcoiling of organic molecules under hydrophobic-lipophilic interaction(HLI) between the excited carbazole chromophore and the acceptor.Since the similar effects are observed even when the concentration of the probes are less than their CAgCs(critical aggregate concentrations )in the DX-H2O mixture with the same φ values,formation of the intermolecular exciplex has been excluded.The effects are found to be strongly depended on φ values,indication that they are mainly driven by HLI.The properties of the acceptors can also affect the intramolecular exciplex formation.With terephthalic acid methylester moiety as the acceptor,the carbazole chromophore exhibits the fluorescence spectra of the exciplex,while with 3,5-dinitrobenzoate moiety as the acceptor,only the fluorescence spectra of excited carbazolyl chromophore are observed.     

INTERACTION OF POLYVINYLPYRROLIDONE WITH METAL CHLORIDE AQUEOUS SOLUTIONS

Interactions of polyvinylpyrrolidone (PVP) with metal chlorides (MgCl2, CaCl2, KC1 and BaC12) have been investigated by viscometric and spectrophotometric techniques in aqueous solutions. Intrinsic viscosity [η] of (PVP) has shown a discontinuity with varying concentration of metal chlorides. The decreasing order of effectiveness of cation is K1 ＞Ca2 ＞ Mg2 ＞ Ba2 for poly(vinylpyrrolidone) solution. Changes in the absorption spectra of the cosolutes were observed in the presence of PVP in the lower limit of the UV-visible region i.e. 200-210 nm. These changes were attributed to interaction of PVP molecules with the cosolute molecules. As the concentration of the cosolute increased, a red shift in the peaks was observed, indicating an increase in interaction between PVP and cosolutes.     

Hydrogen bonding interactions between ethylene glycol and water: density,excess molar volume,and spectral study

Studies of the density and the excess molar volume of ethylene glycol (EG)-water mixtures were carried out to illustrate the hydrogen bonding interactions of EG with water at different temperatures. The re-sults suggest that a likely complex of 3 ethylene glycol molecules bonding with 4 water molecules in an ethylene glycol-water mixture (EGW) is formed at the maximal excess molar volume,which displays stronger absorption capabilities for SO2 when the concentration of SO2 reaches 400×10?6 (volume ratio) in the gas phase. Meanwhile,FTIR and UV spectra of EGWs were recorded at various EG concentra-tions to display the hydrogen bonding interactions of EG with water. The FTIR spectra show that the stretching vibrational band of hydroxyl in the EGWs shifts to a lower frequency and the bending vibra-tional band of water shifts to a higher frequency with increasing the EG concentration,respectively. Furthermore,the UV spectra show that the electron transferring band of the hydroxyl oxygen in EG shows red shift with increasing the EG concentration. The frequency shifts in FTIR spectra and the shifts of absorption bands in UV absorption spectra of EGWs are interpreted as the strong hydrogen bonding interactions of the hydrogen atoms in water with the hydroxyl oxygen atoms of EG.     

ab initio calculation study on vibrational spectra of C_2B_(10)H_(12),NB_(11)H_(12) and C_2B_(10)H_(11)Cl

Geometrical optimization and theoretical calculation of the vibrational frequencies have been performed for C2B10H12, NB11H12 and C2B10Cl by using Gaussian 92 program at 6-31G basis set. The results obtained in this work are in agreement with experimental ones. The optimized geometry and vibrational spectra show that the icosahedral configuration remains unchanged upon converting from B12H122- to the title compounds. The vibrational spectrum of C2B10H11Cl features the absence of C-Cl stretching vibration. But the (C2B10H11)-Cl vibration mode in the low frequency region is as the case for two-atom molecules if the group (C2B10H11) is considered as a pseudoatom     

Application of Lie algebraic method to the calculation of rotational spectra for linear triatomic molecules

The Hamiltonian describing rotational spectra of linear triatomic molecules has been derived by using the dynamical Lie algebra of symmetry group U1(4) U2(4). After rovibrational interactions being considered, the eigenvalue expression of the Hamiltonian has the form of term value equation commonly used in spectrum analysis. The molecular rotational constants can be obtained by using the expression and fitting it to the observed lines. As an example, the rotational levels of v2 band for transition (02°0-0110) of molecules N2O and HCN have been fitted and the fitting root-mean-square errors (RMS) are 0.00001 and 0.0014 cm-1, respectively.     

可反应表面修饰银纳米颗粒的制备与结构表征

Surface reactable modified silver nanoparticles were prepared by NaBH4 reduced silver ion in the aquenous solvent, in the presence of the double group modifying agent, O,O′-di(11-bromic undecane)dithiophosphonic acid. The morphology and structure of the product were characterized using Transmission Electron Microscope(TEM), UV-Visible Absorption(UV-Vis) spectra, Fourier Transform Infrared(FTIR) spectra. The result indicate that the products are spherical shape and no aggregation, C-Br functional groups are on the outermost portion of the silver nanoparticles. The nanoparticles were well dispersed in organic solution, such as chloroform, petroleum ether, toluene etc. The analysis of the sample which reacted with trimethylamine by X-ray photoelectron spectra(XPS) shows the silver nanoparticles can undergo many reactions.     

STUDY OF XPS AND EHMO CALCULATION ON SILATRANE COMPOUNDS

Twenty silatrane compounds with different substituents(R) on the silicon atom are studied by means of X-ray photoelectron spectroscopy(XPS) and EHMO(extended Hückel molecular orbitals) theoretical calculation of the nine compounds in which substituents(R), F, Cl, Br, I, CH_3, H, CH=CH_2, CH_2Cl and CHCl_2, are carried out. By the X-ray photoelectron spectra of the component elements in these compounds, the existence of N→Si dative bond in these molecules is not only confirmed, but the affection of the different substituents on the strength of N→Si dative bond is also obtained. A linear correlation exists between atomic netcharge(Q) obtained by EHMO calculation and the binding energy shifts of N_1_g and Si_(2p) due to different substituents. The calculated bond orders can well predict the effect ou the strength of N→Si dative bond due to the change of substituents in the experiment. Meanwhile, the calculations indicate that the strength of N→Si dative bond in molecules of all substituents is about h     

Study on the atmospheric photochemical reaction of CF_3 radicals using ultraviolet photoelectron and photoionization mass spectrometer

A study of the atmospheric photochemical reaction of CF3 radical with CO and O2 was performed by using a homemade ultraviolet photoelectron spectrometer-photoionization mass spectrometer (PES- PIMS). The electronic structures and mechanism of ionization and dissociation of CF3OC(O)OOC(O)- OCF3 were investigated. It was indicated that the two bands on the photoelectron spectrum of CF3OC(O)OOC(O)OCF3 are the result of ionization of an electron from a lone pair of oxygen and a fluo- rine lone pair of CF3 group. The outermost electrons reside in the oxygen lone pair. The experimental and theoretical first vertical ionization energy is 13.21 and 13.178 eV, respectively, with the PES and OVGF method. They are in good agreement. The photo ionization and dissociation processes were discussed with the help of theoretical calculations and PES-PIMS experiment. After ionization, the parent ions prefer the dissociation of the C-O bond and giving the fragments CF3OCO and CF3 . It demonstrated that the ultraviolet photoelectron and photoionization mass spectrometer could be ap- plied widely in the study of atmospheric photochemical reaction.     

Effect of urea on synchronous fluorescence spectra and electrochemical behaviour of cytochrome

The changes of the synchronous fluorescence spectra and the electrochemical behaviour of cytochrome c with the urea concentration are studied. It has been found that with the increase of urea concentration, there occur sequentially the deaggregation of cytochrome c molecules, the increase of exposure extent of the heme group to the solvent, the disruption of Fe-S bond of the heme group and the change in the electrochemical behaviour of cytochrome c. It is suggested that the reason why the electrochemical reaction of cytochrome c is irreversible is that cytochrome c molecules exist in the concentrated solution as oligomers which are electrochemically inactive.     

Preparation and characterization of vanadium(IV) oxide supported on SBA-15 and its catalytic performance in benzene hydroxylation to phenol using molecular oxygen

Preparation of dispersed transition metal oxides catalyst with low oxidation state still remains a challenging task in heterogeneous catalysis.In this study,vanadium oxides supported on zeolite SBA-15 have been prepared under hydrothermal condition using V 2 O 5 and oxalic acid as sources of vanadium and reductant,respectively.The structures of samples,especially the oxidation state of vanadium,and the surface distribution of vanadium oxide species,have been thoroughly characterized using various techniques,including N 2-physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV-visible spectra(UV-Vis) and UV-visible-near infrared spectra(UV-Vis-NIR).It is found that the majority of supported vanadium was in the form of vanadium(IV) oxide species with the low valence of vanadium.By adjusting hydrothermal treatment time,the surface distribution of vanadium(IV) oxide species can be tuned from vanadium(IV) oxide cluster to crystallites.These materials have been tested in the hydroxylation of benzene to phenol in liquid-phase with molecular oxygen in the absence of reductant.The catalyst exhibits high selectivity for phenol(61%) at benzene conversion of 4.6%,which is a relatively good result in comparison with other studies employing molecular oxygen as the oxidant.     

INFRARED SPECTRA AND X- RAY DIFFRACTION ANALYSIS OF TAUTOMER AND CONFORMATIONS OF HEXAHYDRO- THIADIAZA-PHOSPHORIN-5 ONES

<正> The structures of hexahydro-2-aryloxy-2-thiono-3-methyl 1,3,4,2-thiadiazaphosphorin-5-ones have been studied by means of IR spectra and X-ray diffraction method. The IR spectra show that the C=O absorption of the keto-form(la) is near 1715cm-1 and C=N absorption of enol-form near 1660cm-1. The crystals are monoclinic with space group P21/a,a= 14. 029(3) ,b=8. 353(2) ,c=23. 353(6) A ,β= 107. 01 2)°. There are four pairs of molecules in keto- (1a) and enol-form (1b) per unit cell. The C=O and C(2)- N(2) distances of keto-form are 1. 21 and 1. 37 A Respectively, While the C(2)-O and C(2) = N(2) distances of enol-form 1. 316 and 1. 326A respec-evely. The rings of hexahydro-1,3,4,2-thiadiazaphosphorine for keto- and enol-form are toth in boat conformation.     

1D Lanthanide Coordination Polymers Based on 3-（Pyridin-4,yl）benzoic Acid： Syntheses, Structures and Luminescent Properties

Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(H2O)2· H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoclinic system, space group P1. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.     

CONFORMATIONAL CHANGE IN MESOGENIC CORES OF DISCOTIC LIQUID CRYSTALS

Infrared spectra of bis(β-diketonato) copper(Ⅱ) complex liquid crystals with different flexible chain lengths(the carbon number =12 and 14) have been studied as a function of temperature. Conformational changes in mesogenic cores of the molecules have been characterized by using the out-of-plane bending vibration mode of aromatic C-H bonds. The result shows that for the phenylene rings and the chelate rings of the molecules there occurred an enhancement of extended conjugation of the two π-electron systems during phase transitions, which was also supported by UV measurements. It suggests that the big quasi-planar core structure in the discotic complex consisted of four phenylene rings and the central chelate rings is not maintained in every phase.     

An Ab initio Theoretical Study on the Nonadiabatic Coupling for Na＋I2 Collision System

The ionic and neutral state potential energy surfaces (PESs) of Na I2 collision system have been calculated on QCISD(T) level by using ab initio method.The location and depth of the potential well,the collision radius and their fine structures have been analyzed at the equilibrium geometry of I2 molecule.The electronic transfer probabilities are also calculated in terms of Landau-Zener model.The lifetime of scattering resonance state is evaluated by the uncertainty principle.All the results have been compared with those obtained according to the Aten-Lanting-Los PES and Feng‘s PES.