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1.
We present for the first time the elaboration via sol gel route of cerium (1 mol%) doped SrHfO3 powders and films. The sol is elaborated using hafnium and strontium ethoxides as precursors and cerium nitrate as dopant. The structure of powders and films are characterized by convergent methods: Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, Raman spectroscopy and optical measurements conducted by the prism coupling method. The powder crystallises from amorphous to pure SrHfO3 orthorhombic perovskite phase after a 800°C heat treatment. Nevertheless HfO2 monoclinic phase coexists with orthorhombic perovskite phase after a 1000°C heat treatment. The film is amorphous for annealing temperatures lower than 700°C and presents good waveguiding performances. The film heat-treated at 700°C exhibits a refractive index of 1.810 ± 0.001 (λ = 543.5 nm) for a thickness around 375 nm. The attenuation coefficient obtained on the 400°C heat-treated film is α = 4.0 ± 0.5 dB/cm (λ = 632.8 nm). The film starts to crystallize at 750°C into the SrHfO3 orthorhombic phase but HfO2 monoclinic phase is also detected after a heat treatment at 1000°C. The potentiality of sol gel Ce3+:SrHfO3 powders and films for scintillation applications are investigated.  相似文献   

2.
The ultraviolet absorption spectrum of CF3CFClO2 and the kinetics of the self reactions of CF3CFCl and CF3CFClO2 radicals and the reactions of CF3CFClO2 with NO and NO2 have been studied in the gas phase at 295 K by pulse radiolysis/transient UV absorption spectroscopy. The UV absorption cross section of CF3CFCl radicals was measured to be (1.78 ± 0.22) × 10?18 cm2 molecule?1 at 220 nm. The UV spectrum of CF3CFClO2 radicals was quantified from 220 nm to 290 nm. The absorption cross section at 250 nm was determined to be (1.67 ± 0.21) × 10?18 cm2 molecule?1. The rate constants for the self reactions of CF3CFCl and CF3CFClO2 radicals were (2.6 ± 0.4) × 10?12 cm3 molecule?1 s?1 and (2.6 ± 0.5) × 10?12 cm3 molecule?1 s?1, respectively. The reactivity of CF3CFClO2 radicals towards NO and NO2 was determined to (1.5 ± 0.6) × 10?11 cm3 molecule?1 s?1 and (5.9 ± 0.5) × 10?12 cm3 molecule?1 s?1, respectively. Finally, the rate constant for the reaction of F atoms with CF3CFClH was determined to (8 ± 2) × 10?13 cm3 molecule?1 s?1. Results are discussed in the context of the atmospheric chemistry of HCFC-124, CF3CFClH. © 1994 John Wiley & Sons, Inc.  相似文献   

3.
During the irradiation of WO3 films d = 7–160 nm thick by light at λ = 320 nm (I = (1.5–7) × 1015 quantum cm−2 s−1), absorption band at λ = 850 nm appeared along with absorption band edge shift to shorter waves. The subsequent irradiation of samples at λ = 850 nm caused the disappearance of the longwave absorption band. The intrinsic absorption edge of WO3 films was determined (λ = 320 nm). The degree of transformations of WO3 films increased under atmospheric conditions as the intensity of incident light and the time of irradiation (1–140 min) grew and as film thickness decreased. A mechanism of photochemical transformations of WO3 films was suggested. This mechanism included the generation of electron-hole pairs, the recombination of part of nonequilibrium charge carriers, the formation of [eVa2+e] centers, and the isolation of photolysis products.  相似文献   

4.
The ultraviolet absorption spectra and self reaction kinetics of CF3CCI2 and CF3CCI2O2 radicals have been studied in the gas phase at 295K. Absorption cross sections were quantified over the wavelength range 220–300 nm. Measured cross sections near the absorption maxima were γCF3CCI2(230 nm) = (9.70 ± 1.47) x 10-18 and γCF3CCI2O2(250 nm) = (1.70 ± 0.26) x 10-18 cm2 molecule-1. Errors are statistical (2γ) together with our estimate of potential systematic errors. Rate constants for the self reaction of CF3CCI2 and CF3CCI2O2 radicals were measured to be k6 = (2.46 ± 0.43) x 10-12 and k7obs = (3.33 ± 0.53) x 10-12 cm3 molecule-1 s-1, respectively. Results are discussed with respect to the existing database concerning halogenated peroxy radicals.  相似文献   

5.
Irradiation of MoO3 films (with a thickness d = 5–54 nm) with light (λ = 320 nm, I = (1.5–7) × 1015 quantum cm?2 s?1) led to the formation of an absorption band at λ = 870 nm along with the shift of the edge of the absorption band to the short-wave region of the spectrum. Further irradiation of the samples with light at λ = 870 nm caused diffusion of the long-wave absorption band. The conversion of MoO3 films increased when the incident light intensity and irradiation time increased and the film thickness decreased under the atmospheric conditions. A mechanism of the photochemical transformation of MoO3 films was suggested. It involves the generation of electron-hole pairs, recombination of some nonequilibrium charge carriers, formation of [(e(V a )++ e] centers, and isolation of photolysis products.  相似文献   

6.
The gas phase photodissociation spectra of four protonated β-diketones were obtained and compared with the absorption spectra of the corresponding ions in solution. Protonated 2,4-pentanedione was observed to undergo the photodissociation process [C5H9O2]+ +hν → [CH3CO]+ +C3H6O with a λmax at 276±10 nm compared with a solution absorption maximum at 286 nm. Protonated 2,4-hexanedione was observed to undergo the photodissociation processes [C6H11O2]+ +hν → [CH3CO]+ +C4H8O and [C6H11O2]+ +hν → [C2H5CO]+ +C3H6O with a λmax at 279±10 nm compared with a solution absorption maximum at 288 nm. Protonated 3-methyl-2,4-pentanedione was observed to undergo the photodissociation process [C6H11O2]+ +hν → [CH3CO]+ +C4H8O with a λmax at 295±10 nm compared with a solution absorption maximum at 305 nm. Protonated 1,1,1-trifluoro-2,4-pentanedione was observed to undergo the photodissociation process [C5H6F3O2]+ +hν → CF3H+[C4H5O2]+ with a λmax at 273±10 nm compared with a solution absorption maximum at 288 nm. The [CH3CO]+ and [C2H5CO]+ produced photochemically with the first three ions react to regenerate the protonated β-diketone leading to a photostationary state. Photodissociation of the protonated alkyl β-diketones is believed to occur from the protonated keto form, whereas photodissociation of protonated 1,1,1-trifluoro-2,4-pentanedione is believed to occur from the protonated enol form. Mechanisms for the observed photodissociation processes are proposed and comparisons with results from related techniques are presented.  相似文献   

7.
The UV absorption spectrum and kinetics of CH2I and CH2IO2 radicals have been studied in the gasphase at 295 K using a pulse radiolysis UV absorption spectroscopic technique. UV absorption spectra of CH2I and CH2IO2 radicals were quantified in the range 220–400 nm. The spectrum of CH2I has absorption maxima at 280 nm and 337.5 nm. The absorption cross-section for the CH2I radicals at 337.5 nm was (4.1 ± 0.9) × 10?18 cm2 molecule?1. The UV spectrum of CH2IO2 radicals is broad. The absorption cross-section at 370 nm was (2.1 ± 0.5) × 10?18 cm2 molecule?1. The rate constant for the self reaction of CH2I radicals, k = 4 × 10?11 cm3 molecule?1 s?1 at 1000 mbar total pressure of SF6, was derived by kinetic modelling of experimental absorbance transients. The observed self-reaction rate constant for CH2IO2 radicals was estimated also by modelling to k = 9 × 10?11 cm3 molecule?1 s?1. As part of this work a rate constant of (2.0 ± 0.3) × 10?10 cm3 molecule?1 s?1 was measured for the reaction of F atoms with CH3I. The branching ratios of this reaction for abstraction of an I atom and a H atom were determined to (64 ± 6)% and (36 ± 6)%, respectively. © 1994 John Wiley & Sons, Inc.  相似文献   

8.
This work reports the study the structure, optical and magnetic properties of LaFeO3 nanoparticles synthesized by the polymerized complex method. The LaFeO3 nanoparticles were successfully obtained from calcination of the precursor at different temperatures from 750 to 1,050 °C in air for 2 h. The calcined LaFeO3 nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–Visible spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge spectroscopy (XANES) and vibrating sample magnetometry. The XRD and TEM results showed that all LaFeO3 samples had a single phase nature with the orthorhombic structure. The estimated crystallite sizes were in the range of 44.5 ± 2.4–74.1 ± 4.9 nm. UV–Vis spectra showed strong UV and Vis absorption with small band gap energy. The valence states of Fe ions were in the Fe3+ and Fe4+ state, as confirmed by XPS and XANES results. The weak ferromagnetic behavior with specific saturation magnetization of 0.1 emu/g at 10 kOe was obtained for the small particle of 44.5 ± 2.4 nm. The uncompensated spins at the surface was proposed as playing a part in the magnetic properties of small sized LaFeO3.  相似文献   

9.
Laser-flash photolysis of RBr/O3/SF6/He mixtures at 248 nm has been coupled with BrO detection by time-resolved UV absorption spectroscopy to measure BrO product yields from O(1D) reactions with HBr, CF3Br, CH3Br, CF2ClBr, and CF2HBr at 298±3 K. The measured yields are: HBr, 0.20±0.04; CF3Br, 0.49±0.07; CH3Br, 0.44±0.05; CF2ClBr, 0.31±0.06; and CF2HBr, 0.39±0.07 (uncertainties are 2σ and include estimates of both random and systematic errors). The results are discussed in light of other available information or O(1D)+RBr reactions. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 555–563, 1998  相似文献   

10.
Double-scale composite lead zirconate titanate Pb(Zr0.52Ti0.48)O3 (PZT) thin films of 360 nm thickness were prepared by a modified composite sol-gel method. PZT films were deposited from both the pure sol and the composite suspension on Pt/Al2O3 substrates by the spin-coating method and were sintered at 650°C. The composite suspension formed after ultrasonic mixing of the PZT nanopowder and PZT sol at the powder/sol mass concentration 0.5 g mL−1. PZT nanopowder (≈ 40–70 nm) was prepared using the conventional sol-gel method and calcination at 500°C. Pure PZT sol was prepared by a modified sol-gel method using a propan-1-ol/propane-1,2-diol mixture as a stabilizing solution. X-ray diffraction (XRD) analysis indicated that the thin films possess a single perovskite phase after their sintering at 650°C. The results of scanning electron microscope (SEM), energy-dispersive X-ray (EDX), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analyses confirmed that the roughness of double-scale composite PZT films (≈ 17 nm) was significantly lower than that of PZT films prepared from pure sol (≈ 40 nm). The composite film consisted of nanosized PZT powder uniformly dispersed in the PZT matrix. In the surface micrograph of the film derived from sol, large round perovskite particles (≈ 100 nm) composed of small spherical individual nanoparticles (≈ 60 nm) were observed. The composite PZT film had a higher crystallinity degree and smoother surface morphology with necklace clusters of nanopowder particles in the sol-gel matrix compared to the pure PZT film. Microstructure of the composite PZT film can be characterized by a bimodal particle size distribution containing spherical perovskite particles from added PZT nanopowder and round perovskite particles from the sol-matrix, (≈ 30–50 nm and ≈ 100–120 nm), respectively. Effect of the PZT film preparation method on the morphology of pure and composite PZT thin films deposited on Pt/Al2O3 substrates was evaluated.  相似文献   

11.
Photoacoustic (PA) spectra of Ho3+, Er3+, and Sm3+ doped PVA films were obtained in 350–800 nm range. PA spectra were also obtained for the respective dopant oxides: Ho2O3, Er2O3, and Sm2O3 for comparison. It was found that in PVA the PA sensitivity has increased considerably compared to pure rare earth oxides. The relative intensities of absorption bands at 540 and 637 nm of Ho3+: PVA have shown distinct enhancement, indicating the increase in nonradiative relaxation at these excitations. Furthermore, the PA signals at wavelengths for different PA absorption bands were monitored as a function of chopping frequency. These experiments have shown that PA signal varies w−1 both for oxides and PVA samples, suggesting that they behave as thermally thin samples. © 1997 John Wiley & Sons, Inc.  相似文献   

12.
Using a pulse-radiolysis transient UV–VIS absorption system, rate constants for the reactions of F atoms with CH3CHO (1) and CH3CO radicals with O2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF6 was determined to be k1=(1.4±0.2)×10−10, k2=(4.4±0.7)×10−12, and k3=(2.4±0.7)×10−11 cm3 molecule−1 s−1. By monitoring the formation of CH3C(O)O2 radicals (λ>250nm) and NO2 (λ=400.5nm) following radiolysis of SF6/CH3CHO/O2 and SF6/CH3CHO/O2/NO mixtures, respectively, it was deduced that reaction of F atoms with CH3CHO gives (65±9)% CH3CO and (35±9)% HC(O)CH2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH2O radicals via C C bond scission occurs at a rate of <4.7×105 s−1. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 913–921, 1998  相似文献   

13.
UV spectra of SF5 and SF5O2 radicals in the gas phase at 295 K have been quantified using a pulse radiolysis UV absorption technique. The absorption spectrum of SF5 was quantified from 220 to 240 nm. The absorption cross section at 220 nm was (5.5 ± 1.7) × 10−19 cm2. When SF5 was produced in the presence of O2 an equilibrium between SF5, O2, and SF5O2 was established. The rate constant for the reaction of SF5 radicals with O2 was (8 ± 2) × 10−13 cm3 molecule−1 s−1. The decomposition rate constant for SF5O2 was (1.0 ± 0.5) × 105 s−1, giving an equilibrium constant of Keq = [SF5O2]/[SF5][O2] = (8.0 ± 4.5) × 10−18 cm3 molecule−1. The SF5 O2 bond strength is (13.7 ± 2.0) kcal mol−1. The SF5O2 spectrum was broad with no fine structure and similar to the UV spectra of alkyl peroxy radicals. The absorption cross section at 230 nm was found to (3.7 ± 0.9) × 10−18 cm2. The rate constant of the reaction of SF5O2 with NO was measured to (1.1 ± 0.3) × 10−11 cm3 molecule−1 s−1 by monitoring the kinetics of NO2 formation at 400 nm. The rate constant for the reaction of F atoms with SF4 was measured by two relative methods to be (1.3 ± 0.3) × 10−11 cm3 molecule−1 s−1. © 1994 John Wiley & Sons, Inc.  相似文献   

14.
Bi3+ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi3+ and lanthanide ions. Codoping of Bi3+ and Ln3+ (Ln=Er and Yb) in Cs2AgInCl6 double perovskite is presented. Bi3+-Er3+ codoped Cs2AgInCl6 shows Er3+ f-electron emission at 1540 nm (suitable for low-loss optical communication). Bi3+ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi3+-Er3+ codoped Cs2AgInCl6 shows ca. 45 times higher emission intensity compared to the Er3+ doped Cs2AgInCl6. Similar results are also observed in Bi3+-Yb3+ codoped sample emitting at 994 nm. A combination of temperature-dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.  相似文献   

15.
Radiation chemical reactions ofOH, O•−, N3 and e aq t- witho- and m-hydroxycinnamic acids were studied. The second-orderrateconstantsforthereaction ofOH with ortho and meta isomers in buffer solution at pH7 are 3.9±0.2 × 109 and 4.4 ± 0.3 × 109 dm3 mol-1 s-1 respectively. At pH 3 the rate with the ortho isomer was halved (1.6 ± 0.4 × 109 dm3 mol-1 s-1) but it was unaffected in the case of meta isomer (k = 4.2±0.6 × 109dm3mol-1 s-1). The rate constant in the reaction of N3 with the ortho isomer is lower by an order of magnitude (k = 4.9 ± 0.4 × 108 dm3 mol-1s-1). The rates of the reaction of e aq t- with ortho and meta isomers were found to be diffusion controlled. The transient absorption spectrum measured in theOH witho-hydroxycinnamic acid exhibited an absorption maximum at 360 nm and in meta isomer the spectrum was blue-shifted (330 nm) with a shoulder at 390 nm. A peak at 420 nm was observed in the reaction of Obb−with theo-isomer whereas the meta isomer has a maximum at 390 and a broad shoulder at 450 nm. In the reaction of the absorption peaks were centred at 370–380 nm in both the isomers. The underlying reaction mechanism is discussed.  相似文献   

16.
The mechanism and kinetics of the reaction of O(3P) atoms with propane were investigated using molecular modulation spectroscopy, with the O(3P) atoms being generated by the Hg photosensitized decomposition of N2O. The absorption spectrum of the X2II3/2 state of OH was observed in the ultraviolet between 307 and 309 nm, and it was confirmed that OH was the product of the O(3P) reaction with propane. The rate constants for the reactions of O(3P) and OH with propane were determined to be 3.9±0.7±1010 and 1.19±0.05±1012 cm3/mole·sec, respectively, at T=56±5°C.  相似文献   

17.
The kinetics of the self-reactions of HO2, CF3CFHO2, and CF3O2 radicals and the cross reactions of HO2 with FO2, HO2 with CF3CFHO2, and HO2 with CF3O2 radicals, were studied by pulse radiolysis combined with time resolved UV absorption spectroscopy at 295 K. The rate constants for these reactions were obtained by computer simulation of absorption transients monitored at 220, 230, and 240 nm. The following rate constants were obtained at 295 K and 1000 mbar total pressure of SF6 (unit: 10−12 cm3 molecule−1 s−1): k(HO2+HO2)=3.5±1.0, k(CF3CFHO2+CF3CFHO2)=3.5±0.8, k(CF3O2+CF3O2)=2.25±0.30, k(HO2+FO2)=9±4, k(CF3CFHO2+HO2)=5.0±1.5, and k(CF3O2+HO2)=4.0±2.0. In addition, the decomposition rate of CF3CFHO radicals was estimated to be (0.2–2)×103 s−1 in 1000 mbar of SF6. Results are discussed in the context of the atmospheric chemistry of hydrofluorocarbons. © 1997 John Wiley & Sons, Inc.  相似文献   

18.
CH3Br is photodissociated in the first continuum. Dissociation takes place into ground state CH3 and Br [ = Br(2P32] or Br* [ = Br(*P12)]. Time of flight and angular distributions of the CH3 fragments are measured. The Br*/Br ratios upon excitation at 222 and 193 nm are found to be 1.00 and 0.20 respectively. The anisotropy parameters at these wavelengths are β = 0.28±0.04 and β = ?0.23±0.02, respectively. The total absorption cross section is decomposed into partial absorption cross sections of the 1Q, 3Q0 and 3Q1 states. It appears that excitation at 222 nm takes place to the 3Q0 and 3Q 1 states whereas at 193 nm the 1Q and 3Q0 states are excited. Contrary to CH3I, the adiabatic curve crossing between the 3Q0 and the 1Q states in Ch3Br is not important. The dissociation energy of the CBr bond is determined to be D0(CH3Br) = 2.87±0.02 eV.  相似文献   

19.
The reflectivity at normal incidence of single crystals of Na+C222 · Na was measured from 350 to 2500 nm in a microreflectivity apparatus. The reflectivity spectrum shows a single peak at 630 ± 10 nm (1.97 eV) with a peak reflectivity of up to 60%. No rise in the reflectivity was found toward longer wavelengths. This absence of a plasma edge confirms that the concentration of conduction electrons is smaller than 1.8 × 1020/cm3 as expected from the low electrical conductivity of this sodide. The absorption spectrum of thin solid films of Na+C222 · Na, formed by vapor deposition, was measuredin situ in a vacuum evaporator. The absorption peak was at 650 ± 10 nm (1.91 eV), with a full-width at half-maximum of 0.37 eV. The reflectivity and absorption data were used together to estimate the indices of refraction and absorption and the components of the complex dielectric constant as a function of wavelength.  相似文献   

20.
The UV absorption spectrum and the kinetics of the self combination reaction of the CCl3 radical were studied by flash photolysis in the temperature range 253–623 K. Experiments were performed at the atmospheric pressure, except for a few runs at the highest temperatures, which were performed between 30 and 760 torr. CCl3 radicals were generated by flash photolysis of molecular chlorine in the presence of chloroform. The UV spectrum exhibits a strong unstructured band between 195 and 260 nm with a maximum at 211 ± 2 nm. The absorption cross section, measured relative to σ(HO2), is σ(CCl3) = (1.45 ± 0.35) × 10?17 cm2 molecule?1 at the maximum. This value takes into account the uncertainty in σ(HO2) which was taken equal to (4.9 ± 0.7) × 10?18 cm2 molecule?1. The absolute rate constant for the CCl3 mutual combination was determined by computer simulation of the transient decays. The rate constant, which exhibits a slight negative temperature coefficient, can be expressed as: The study of the pressure dependence showed that only a slight fall-off behavior could be observed at the highest temperature (623 K). This result was corroborated by RRKM calculations which showed that the rate constant is at the high pressure limit under most experimental conditions below 600 K.  相似文献   

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