飞秒激光场中甲醇产物离子的角分布

利用直流切片离子成像技术结合飞行时间质谱技术,我们研究了甲醇(CH_3OH)分子在800 nm飞秒激光场中的多光子解离和库仑爆炸过程.获得了甲醇分子在光场中的飞行时间质谱和产物离子的切片影像,分析得到了不同库仑爆炸通道碎片离子的动能分布和角度分布.本文对比分析了C-O键断裂产生H_2O~+的H转移通道和产生OH~+的非H转移通道的角分布,计算了不同激光强度下两个通道的各向异性参数α_2和(cos~2θ),并根据产物离子角度分布与激光强度和离子价态的关系,揭示了甲醇分子在飞秒光场中的准直机制为动力学准直.     

Photo-induced degradation of Ru（Ⅱ） complex absorbed on anatase TiO2 thin film electrode

Photo-induced degradation of a monolayer of Ru（Ⅱ） complex absorbed on anatase TiO2 thin film was studied by using resonant micro-Raman spectroscopy. Under intense light radiation of a laser and in the absence of a reducing agent, the dye decomposed quickly. When the dye-sensitized TiO2 thin film electrode was covered by a reducing agent, namely the I^-/I3^- redox couple, the photo-induced decomposing rate was slowed by a factor of -10^6. In both cases, the dye decomposed with time under an exponential law.     

Decay dynamics of excited CS<Subscript>2</Subscript> and NH<Subscript>3</Subscript> investigated by femtosecond laser

By using the home-made femtosecond laser system and the time-of-flightmass spectrometer, the decay dynamics of excited carbon disulfide (CS2) and ammonia (NH3) are investigated in real time by pump-probe multiphoton ionization detection. The estimated lifetime constant of the NH3 state (514 fs) agreed quite well with the literature report. For the first time, the decay lifetime constants of the NH3 ′1A′1 state (93793 fs), the CS2 state (153 ± 10 fs), and the CS2 Rydberg state[2-3]6sσg(3Ⅱg)(948 ± 23 fs) are obtained.     

Preparation and upconversion luminescence of YVO<Subscript>4</Subscript>:Er<Subscript>3+</Subscript>, Yb<Subscript>3+</Subscript>

YVO₄:Er³⁺, Yb³⁺ with varying Yb³⁺ concentrations were prepared by a precipitation method. The results of X-ray diffraction (XRD) show that all the samples have a tetragonal zircon structure; the calculated average crystallite sizes are in the range of 14–22 nm. The lattice constants and cell volume of the samples decrease slightly with the increase in Yb³⁺ concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green emission is observed, which is attributed to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transitions of Er³⁺, and the red emission peaks in 650–675 nm can be ignored. The emission intensity for the sample depends on the Yb³⁺ concentration. These results reveal that the upconversion processes of YVO₄:Er³⁺, Yb³⁺ are related to the structure and the doping Yb³⁺ concentration of the sample.     

Intense laser induced field ionization of C<Subscript>2</Subscript>H<Subscript>2</Subscript>, C<Subscript>2</Subscript>H<Subscript>4</Subscript>, and C<Subscript>2</Subscript>H<Subscript>6</Subscript>

Using HOMO Field Ionization Model, the tunneling probabilities and the theoretical threshold intensities of the field ionizations of acetylene, ethylene, and ethane in intense laser field are calculated. C2H2, C2H4, and C2H6 were irradiated by 800 nm, 100 fs laser pulses with the intensity range of 10^13-10^14 W/cm^2. A TOF-mass spectrometer was coupled to the laser system and used to experimentally investigate the field ionization of these molecules. The experimental ionization threshold intensities are obtained. The calculating results of the three molecules agree well with the experimental results, indicating that HOMO Field Ionization Model is valid for the ionization of polyatomic molecules in intense laser field.     

Near-infrared to visible up-conversion emissions of Er^3＋ doped Al2O3 powders derived from the sol-gel method

The Er3 doped Al2O3 powders were prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3.5H2O]. The different phase structure, including three crystalline types of (Al,Er)2O3 phases, γ, θ, α, and two Er-Al-O phases, ErAlO3 and Al10Er6O24, was obtained with the 1 mol% Er3 doped Al2O3 powders at the different sintering temperatures of 600―1200℃. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the 2H11/2, 4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3 , were detected by a 978 nm semiconductor laser diodes excitation. The phase structure and OH content had evident influence on the up-conversion emissions intensity. The maximum intensities of both the green and red emissions were obtained respectively for the Er3 doped Al2O3 powders sintered at 1200 ℃, which was composed mainly of α-(Al,Er)2O3, less of ErAlO3 and Al10Er6O24 phases, and with the least OH content. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er3 doped Al2O3 powders.     

Electrochemical properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.3</Subscript>Ti<Subscript>0.2</Subscript>O<Subscript>4</Subscript>/Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> cells

Spinel compounds LiNi_0.5Mn_1.3Ti_0.2O₄ (LNMTO) and Li₄Ti₅O₁₂ (LTO) were synthesized by different methods. The particle sizes of LNMTO and LTO are 0.5–2 and 0.5–0.8 μm, respectively. The LNMTO/LTO cell exhibits better electrochemical properties at both a low current rate of 0.2C and a high current rate of 1C. When the specific capacity was determined based on the mass of the LNMTO cathode, the LNMTO/LTO cell delivered 137 mA·h·g⁻¹ at 0.2C and 118.2 mA·h·g⁻¹ at 1C, and the corresponding capacity retentions after 30 cycles are 88.5% and 92.4%, respectively.     

Up-conversion luminescence of Er^3＋ doped and Er^3＋/Yb^3＋ co-doped YTaO4

The synthesis and up-conversion luminescent properties of YTaO4：Er^3＋ and YTaO4：Er^3＋/Yb^3＋ are reported for the first time. According to the measurement results of up-conversion spectra, Yb^3＋ co-doping can remarkably enhance the green （^2H11/2/^4S3/2→^4I15/2） and red （^4F9/2→^4I15/2） emissions, but depress the infrared emission （^4I9/2→^4I15/2）. With the increase of the Yb^3＋ concentration, the intensity of green emission increases, after that, when the Yb^3＋ concentration increases continuously, the intensity of green emission decreases, while those of the red and infrared emissions increase and decrease alternately. In addition, the up-conversion mechanisms of Er^3＋ doped and Er^3＋/Yb^3＋ co-doped YTaO4 are also discussed. It is found that the transform of up-conversion mechanism from two-step energy transfer to cooperating sensitization takes place when Yb^3＋ concentration is increased up to 12 mol%. With the further increase of Yb^3＋ concentration, the energy-back-transfer gradually becomes the dominant up-conversion mechanism, which results in the quenching of the green emission and slight increasing of the red and infrared emissions.     

Photoluminescence and cathodoluminescence properties of a novel CaLaGa307：Dy3＋ phosphor

A single host white emitting phosphor, CaLaGa3O7:Dy3+, was synthesized by chemical co-precipitation. Field emission scanning electron microscopy, X-ray diffraction, laser particle size analysis, and photoluminescence and cathodoluminescence spectra were used to investigate the structural and optical properties of the phosphor. The phosphor particles were composed of microspheres with a slight tendency to agglomerate, and an average diameter was of about 1.0 μm. The Dy3+ ions acted as luminescent centers, and substituted La3+ ions in the single crystal lattice of CaLaGa3O7 where they were located in Cs sites. Under excitation with ultraviolet light and a low voltage electron beam, the CaLaGa3O7:Dy3+ phosphor exhibited the characteristic emission of Dy3+ (4F9/2-6H15/2 and 4F9/2-6H13/2 transitions) with intense yellow emission at about 573 nm. The chromaticity coordinates for the phosphor were in the white region. The relevant luminescence mechanisms of the phosphor are investigated. This phosphor may be applied in both field emission displays and white light-emitting diodes.     

The giant magnetocaloric effect in Gd<Subscript>5</Subscript>Si<Subscript>2</Subscript>Ge<Subscript>2</Subscript> with low purity gadolinium

The giant magnetocaloric effect Gd5Si2Ge2 alloy was prepared with 99wt% low purity commercial Gd. Powder XRD and magnetic measurements showed that the Gd5Si2Ge2 alloy annealed at 1200℃ for 1h had a significant magnetic- crystallographic first order phase transition at about 270 K. The maximal magnetic entropy change is 17.55 J· kg^-1· K^-1 under a magnetic field change of 0-5 T. The distinct increase of magnetic entropy change belongs to the first-order phase transition from the orthorhombic Gd5Si4-type to the monoclinic Gd5Si2Ge2-type after high temperature heat-treatment.     

Synthesis, Characterization and Calorimetry of Ni（C4H8N2O3）2Cl2

A coordination complex was synthesized from NiCl2 and dipeptide glycylglycine（GG）. It was characterized by element analysis, NMR and TG methods, and then was determined to be Ni（C4HsN2O3）2Cl2. Using an isoperibolic reaction calorimeter, the standard molar enthalpy of formation of Ni（GG）2Cl2（solid） has been determined to be -（1 674.66±2.02） kJ · mol^-1 at 298.15 K.     

I-doping of anodized TiO<Subscript>2</Subscript> nanotubes using an electrochemical method

In order to obtain TiO2 with high photocatalytic activity, a cathode reduction was used to dope I⁷⁺ and I⁵⁺ into TiO₂ nanotubes of anodized Ti in C₂H₂O₄•2H₂O + NH₄F electrolyte. SEM images show that the anodization method integrated the preparation with the doping process, which for nonmetals-doping is advantageous to maintain the morphological integrity of TiO₂ nanotubes. I⁷⁺-I⁵⁺-doping enhances the UV response of TiO₂ and result in a red-shift. Under UV/visible irradiation, a I⁷⁺-I⁵⁺-doped sample (400°C) showed the highest I_ph and photocatalytic efficiency. A part of I^– in the I⁷⁺-I⁵⁺-doped sample is involved in the UV response, the red-shift and the higher I_ph.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

Covariance analysis of the Coulomb explosion of ammonia induced by intense nanosecond laser at 532 nm

The Coulomb explosion of ammonia clusters induced by nanosecond laser at 532 nm with an intensity of ～1012 Wcm^-2 has been studied by time of flight mass spectrometry. The dominant multiply charged ions are N^3＋ and N^2＋ with kinetic energies of 110 and 50 eV respectively. The electrons generated from the multiphoton ionization are heated through inverse bremsstrablung by tbe laser field when colliding with neutral or ionic particles. When their energies surpass the corresponding ionization potentials of the molecules or ions, the subsequent electron impact ionization may take place thus resulting in multi-charged nitrogen ions. Covariance analysis is made to study the possible pathways of the Coulomb explosion.     

High-temperature synthesis in nonpolar solvent for CsPbBr<Subscript>3</Subscript> and CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>PbBr<Subscript>3</Subscript> perovskite nanocrystals with high-efficient luminescence

We report a method to synthesize both organicinorganic CH₃NH₃PbBr₃ and all-inorganic CsPbBr₃ perovskite nanocrystals in nonpolar solvent at high temperature. The cesium oleate and CH₃NH₃Br (MABr) are prepared and then injected into the nonpolar solvent of octadecene including oleic acid, oleylamine, and lead halide. In the synthesis of organic-inorganic perovskites of CH₃NH₃PbBr₃, the frequently-used polar solvent of dimethylformamide or other polar solvents are not used. The prepared CsPbBr₃ nanocrystals are spherical nanoparticles with the diameter of 250 nm. The CH₃NH₃PbBr₃ perovskites are micro- scale hexagonal nanoplatelets. The colloidal perovskites exhibit high-efficient fluorescence and excellent stability.     

Electronic structures and nonlinear optical properties of XAuPH<Subscript>3</Subscript>

The studies on model systems XAuPH3(X-H,F,Cl,Br,I,CN,CH3)have been carried out by using ab intiol HF and DFT B3LYP methods at pseudopotential and double-zeta LANL2DZ level.The results are compared with those of MP2,The properties of the models.i.e.the atomic net charge populations.the frontier molecular orbitals and nonlinear optical(NLO)properties have been investigated under an applied electric field on the basis of optimized structures.The computational results show that for these models characterized as electron acceptor-metal-electron donor(A-M-D)system,the NLO properties are due to intramolecular charge-transfer interaction between the acceptor and the donor.The more charges transfer gives,the better NLO properties.In the selected model systems,IAuPH3 has the biggest βvec and γof 1184.1942 a.u.and 17341.9214 a.u.,whereas IC6H4PH3^ ,A TYPICAL a-π-D organic conjugated system,has βvec and γof 710.7697 and 11664.1405 a.u.respectively.In comparison.IAuPH3 has significant NLO properties.     

Photoluminescence and cathodoluminescence properties of CaLaGa<Subscript>3</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript> phosphors

The CaLaGa₃O₇:Eu³⁺ phosphor was prepared by a chemical co-precipitation method. Field emission scanning electron microscopy (FE-SEM), laser particle size analysis, X-ray diffraction (XRD), photoluminescence (PL), and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphor. The results revealed that the phosphor was composed of microspheres with a slight agglomerate phenomenon and was spherically shaped. The average grain size was about 1.0 μm. Eu³⁺ ions, as luminescent centers, substituted La³⁺ ions into the single crystal lattice of CaLaGa₃O₇ with the sites of C_s. Although the CL spectrum was greatly different from the PL spectrum, it had the strongest red emission corresponding to the ⁵D₀ →⁷F₂ transition of Eu³⁺. Under the excitation of UV light (287 nm) and electron beams (1.0–7.0 kV), the chromaticity coordinates of the phosphor were found to be in the nearly red and orange light regions, respectively.     

Chemical quenching and inhibition of positronium in Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

The pore structure of Cr2O3/Al2O3 catalysts and the surface chemical properties of these pores were characterized by positron lifetime and coincidence Doppler broadening (CDB) measurements. Four lifetime components could be resolved from the positron lifetime spectrum, with two long lifetime components and two short lifetime components. The two long lifetimes τ4 and τ3 are attributed to ortho-positronium (o-Ps) annihilation in large pores and microvoids, respectively. With increasing Cr2O3 content, both τ4 and its intensity I4 show sharp decrease, while τ3 and its intensity I3 keep nearly unchanged. The Doppler broadening S parameters also show sharp decrease with increasing Cr2O3 content. Detailed analysis of the CDB spectrum reveals that the parapositronium (p-Ps) intensity also decreases with increasing Cr2O3 content. This indicates that the change of o-Ps lifetime τ4 is due to the chemical quenching by Cr2O3 but not spin-conversion of positronium. The decrease of o-Ps intensity I4 indicates that Cr2O3 also inhibits positronium formation.     

Giant magneto-optical faraday effect of nanometer Fe-In<Subscript>2</Subscript>O<Subscript>3</Subscript> granular films

The giant magneto-optical Faraday effect of nanometer ferromagnetic metal-semiconductor matrix Fe-ln2O3 granular films prepared by the radio frequency sputtering are studied. The result shows that the Faraday rotation angle θF value of the granular film samples with Fe volume fraction x = 35% is of the order of 10^5（°）/cm at room temperature. Temperature dependence of the Faraday rotation angle θF of Fe0.35（In2O3）0.65 granular films shows that θF value below 10 K increases rapidly with the decrease of the temperature, and when T= 4.2 K, θF value is 106（°）/cm. Through the study of the dependence of low field susceptibility on temperature and the hysteresis loops at different temperatures, it has been found that when the temperature decreases to a critical point Tp = 10 K, the transformation of state from ferro-agnetic to spin-glass-like occurs in Fe0.35（In2O3）0.65 granular films. The remarkable increase of the Faraday rotation angle θF value of Fe0.35（In2O3）0.65 granular films below 10 K seems to arise from the sp-d exchange interaction of the granular film samples in the spin-glass-like state.     

Synthesis and characterization of wormhole-like mesoporous Ce0.6Zr0.35Y0.05O2 solid solutions

Nanoparticles of Ce0.6Zr0.35Y0.05O2 (CZY) solid solution have been prepared by the CTAB (hexadecyl-trimethyl ammonium bromide), CTAB-EG (ethylene glycol) templating, and CTAB-EG-NaCl (in which the pores of the precursor synthesized by the CTAB-EG method is filled by a certain amount of NaCl) method, respectively. The physical properties of these materials were characterized by means of tech-niques such as X-ray diffraction (XRD), high resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and N2 adsorp-tion-desorption measurements. The CZY samples synthesized by the above three methods display wormhole-like mesoporous morphology and cubic crystal structures. The materials are narrow in pore size distribution (averaged pore diameter = 5.3―7.1 nm), high in surface areas (95―119 m2/g), and large in pore volumes (0.16―0.18 cm3/g). It has been demonstrated that the introduction of NaCl is capable of retaining the pore structures of solid nanomaterials at high-temperature calcination.