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1.
The radiative and Forster type of energy transfer processes in a dye mixture laser of 7-diethylamino-4-methyl coumarin (donor) and fluorescein disodium salt (acceptor) under nitrogen laser pumping were investigated. The Forster transfer rate calculated from the absorption and emission spectra of acceptor and donor is 1.3 × 1011 liter mole?1sec?1. The gain of acceptor at 550 nm was measured for acceptor concentrations NA from 10?3M to 3 × 10?3M for a fixed ratio F = 1 of donor to acceptor concentrations at different pump powers. The results agreed with the rate equation model proposed for the dye mixture laser. The radiative rate constant calculated from these results is 3.1 × 1010 liter mole?1sec?1. Numerical simulation of the rate equations showed that the acceptor reaches peak emission with a time lag of 3 ns with respect to the donor peak emission for F = 0.998, NA = 10?5M. This time lag decreases with increasing NA and becomes zero for NA = 10?1M, F = 0.048.  相似文献   

2.
Self-diffusion studies have been performed in the orientationally disordered or the so-called plastic phase of pivalic acid. Single crystals of high purity (99.9999%) containing 109?1010 dislocations m?2 have been used. Thin layers of pivalic acid labelled with 14C or tritium were deposited on sample surfaces. Concentrationpenetration curves were established by serial sectioning. Lattice self-diffusion coefficients D, were measured from 281 to 304.75K. At 281K, the value of D is independent of time. From 281 to 301K, D is given by: D(m2S?1) = (4.9 ± 0.3)10?4 exp [? (59± 1) kJ mole?1/RT].The activation enthalpy of the lattice self-diffusion is roughly equal to the heat of sublimation (Ls = 57 kJ mole?i) and in good agreement with values obtained from NMR. The mass factorf ΔK, where f is the correlation factor and ΔK is a correction factor, has been measured using isotope effect studies. Between 281 and 301K the value obtained is fΔK* 0.1+0.2?0.1  相似文献   

3.
The adsorption and desorption of nitrogen on a platinum filament have been studied by thermal desorption techniques. Nitrogen adsorption becomes significant only after any carbon contamination is removed from the surface by heating the platinum filament in oxygen, and after the CO content in the background gas is reduced substantially. At room temperature nitrogen populates an atomic tightly bound β-state, E = 19 kcal mole?1. The saturation coverage of the (3-state is 4.5 × 1014 atoms cm?2. Formation of the (β-state is a zero order process in the pressure range studied. At 90 K two additional α1- and α2-desorption peaks are observed. The activation energy for desorption for the α2-state is 7.4 kcal mole?1 at low coverage decreasing to 3 kcal mole?1 at saturation of this state, 6 × 10 molecules cm?2. The maximum total coverage in the α-states was 1.2 × 1015 molecules cm?2. A replacement process between the β- and α-states has been observed where each atom in the (β-state excludes two molecules from the α-state.  相似文献   

4.
The interactions between a molecular beam of SiO(g) and a clean and an oxidized tungsten surface were examined in the surface temperature range 600 to 1700 K by mass spectrometrically determined sticking probabilities, by flash desorption mass spectrometry (FDMS) and by Auger electron spectroscopy (AES). The sticking probability, S, of SiO has been determined as a function of coverage and of surface temperature for the clean and the oxidized tungsten surface. Over the temperature range studied and at zero coverage S = 1.0 and 0.88 for the clean and oxidized tungsten surfaces respectively. The results are consistent with both FDMS and AES. For coverage up to one monolayer there is one major adsorption state of SiO on the clean tungsten surface. FDMS shows that Tm = constant (Tm is the surface temperature at which the desorption rate is maximum) and that desorption from this state is described by a simple first order desorption process with activation energy, Ed = 85.3 kcal mole?1 and pre-exponential factor, ν = 2.1 × 1014 sec?1. AES shows that the 92 eV peak characteristic of silicon dominates. In contrast on the oxidized tungsten surface, Tm shifts to higher temperatures with increasing coverage. The data indicate a first order desorption process with a coverage dependent activation energy. At low coverage (θ ? 0.14) there is an adsorption state with Ed = 120 kcal mole?1 and ν = 7.6 × 1019, while at θ = 1.0, Ed = 141 kcal mole?1. This variation is interpreted as due to complex formation on the surface. AES shows that on oxidized tungsten, in contrast to clean tungsten, the dominant peaks occur at 64 and 78 eV, and these peaks are characteristic of higher oxidation states of silicon. Thus, it is concluded that SiO exists in different binding states on clean and oxidized tungsten surfaces.  相似文献   

5.
The time dependence of scintillation intensity from single crystals ofp-terphenyl and mixed crystals ofp-terphenyl and anthracene after bombarding with α-particles was investigated at the two temperaturesT=296 °K andT=92 °K. For the crystals ofp-terphenyl the time dependence of the scintillation anisotropy was also measured. Using the formulas given byKing andVoltz the decay curves ofp-terphenyl were decomposed into two components. Good agreement between experiment and theory was found. The ratio of the prompt intensity to the delayed intensity was determined to be 1∶2 atT=296 °K and 1∶3 atT=92 °K. The diffusion constants for triplet excitons were calculated to beD T(296 °K)≈10?5 cm2 sec?1 andD T(92 °K)≈ 2×10?6 cm2 sec?1, and the triplet-triplet interaction rate constantsχ tt(296 °K)≈ 2.5×10?11 cm3 sec?1 andχ tt(92 °K)≈0.5×10?11 cm3 sec?1.  相似文献   

6.
The diffusion of sulfur in nickel oxide single crystals has been investigated over the temperature range from 1000 to 1250°C. The measured data were found to deviate markedly from the error function complement dependence for diffusion from a constant source. The deviation is attributed to the migration of sulfur by the “double mode simultaneous diffusion mechanism.” The faster mode diffusion is suggested to be via nickel vacancies, and the slower mode diffusion is suggested to be via oxygen vacancies. The diffusivities for faster mode are given by Df = 2.94 exp[? 86.6 kcal/RT] cm2 sec?1 and, the slower mode, Ds = 1.08 × 10?9 exp [?32.8 kcal/RT]cm2sec?1.  相似文献   

7.
Differential and integral molar entropies of the adsorbed layer are calculated from the dependence of the coverage on pressure and temperature published in part I. The experimental entropies correspond up to coverages of 2 × 1014 molecules cm?2 with entropies of the localized adsorption and an additional vibration entropy of about 20 cal deg?1 mole?1 caused by vibrations of the adsorbed atoms in the order of magnitude of 1012 sec?1. At higher coverages the entropy increases and passes through a maximum. This is explained by the formation of a second adsorption state (γ state) probably consisting of molecular hydrogen.  相似文献   

8.
The tip blunting technique to measure the surface self-diffusion of clean metals (A. Piquet, Vu Thien Binh, H. Roux, R. Uzan and M. Drechsler) is extended to study the influence of an adsorption layer on diffusion. The system studied is nickel on tungsten. The increase of the apex radius is measured by means of FEM characteristics. In the temperature range used (1200–1500 K), the nickel monolayer (1.16 × 1015 atoms/cm2) is maintained by compensation of desorbed Ni atoms with a continual flux from an evaporation source. The adsorption life time between 1350 and 1500 K decreases from 850 to 16 s. The conservation of the degree of coverage leads to a method to determine the desorption activation energy of nickel (Ed = 4.56 eV/atom). The surface self-diffusion data of tungsten with a nickel monolayer are found to be D0 = 3 × 10?3cm/2s and Qs = 1.9 eV/atom, compared to the clean tungsten data D0 = 1 cm2/s and Qs = 3.1 eV/atom. The Ni monolayer increases the surface self-diffusion coefficient by a factor 160 at 1200 K and 20 at 1500 K. The results are discussed with respect to nickel activated sintering of tungsten powders.  相似文献   

9.
Positron lifetime spectra and angular correlation curves for seven fine-grained powders of Fe, Co, Ni, and W are analyzed. From the lifetime data, the positron diffusion constant in metals atT=300°K was found to beD +=(1.0±0.5)×10?2 cm2 sec?1. Evidence is presented that positrons are trapped in metal surface states.  相似文献   

10.
We have measured on the CeSn3 compound, the expansion coefficient between 80 and 800 K at normal pressure, the isothermal compressibility in the 0–8 GPa pressure range at room temperature and the heat capacity at constant pressure in the 60–300 K temperature range. The experimental data were compared with those previously found for the isomorphous LaSn3 phase, assumed as a proper reference material for the study of the intermediate valency states in CeSn3. Both the thermal expansion (3α) and the isothermal compressibility (k) of CeSn3 show behaviours quite different from those of LaSn3: for instance, in the standard conditions, 3α is 55 × 10?6K?1for CeSn3 and 38 × 10?6K?1for LaSn3; k is 15 × 10?12 Pa?1 and 12 × 10?12 Pa?1 respectively for CeSn3 and LaSn3. The thermal behaviour of the molar specific heat at constant pressure of CeSn3 is similar to that of LaSn3 for temperatures lower than 50 K. In the 70–300 K temperature range, the heat capacity of CeSn3 is clearly higher than that of LaSn3, ΔCp being maximum near 150 K. The analysis of the calorimetric data show that the electronic coefficient γ of CeSn3 is temperature dependent: its value varies from 53 mJ K?2 mole?1 at low temperature 24 mJ K?2 mole?1 at 300 K.  相似文献   

11.
The scattering of 4.1 Å neutrons by liquid ammonia has been measured at 218 K in the angular range of 30–90° using the Trombay rotating crystal spectrometer. The experimental data, after correcting for multiple scattering, have been compared with model calculations, and it is shown that it is possible to get detailed information about the rotational correlation function on the basis of neutron experiments alone. The model assumes Langevin diffusion for translational motions. Rotational motions are described by means of an orientational correlation function which has a gaseous behaviour for times up toτ 0 and then changes over to a diffusive character with a rotational diffusion constantD r. Within the framework of the model the correlation function can be described withD r=0.28×1013sec?1 andτ 0=0.57×10?18sec. Corrections for multiple scattering and their dependence on model parameters are discussed.  相似文献   

12.
Alkali atoms were scattered with hyperthermal energies from a clean and an oxygen covered (θ ≈ 0.5 ML) W(110) surface. The trapping probability of K and Na atoms on oxygen covered W(110) has been measured as a function of incoming energy (0–30 eV) and incident angle. A considerable enhancement of trapping on the oxygen covered surface compared to a clean surface was observed. At energies above 25 eV there are still K and Na atoms being trapped by the oxygen covered surface. From the temperature dependence of the mean residence time τ of the initially trapped atoms the pre-exponential factor τ0 and the desorption energy Q were derived using the relation: τ = τ0exp(QkTs). On clean W(110) we obtained for Li: τ0 = (8 ± 84) × 10?14sec, Q = (2.78 ± 0.09) eV; for Na: τ0 = (9 ± 3) × 10?14 sec, Q = (2.55 ± 0.04) eV; and for K: τ0 = (4 ± 1) × 10?13 sec, Q = (2.05 ± 0.02) eV. Oxygen covered W(110) gave for Na: τ0 = (7 ±3) × 10?15 sec, Q = (2.88 ± 0.05) eV; and for K: τ0 = (1.3 ± 0.90.6) × 10?14sec, Q = (2.48 ±0.05) eV. The adsorption on clean W(110) has the features of a supermobile two-dimentional gas; on the oxygen covered W(110) adsorbed atoms have the partition function of a one-dimen-sional gas. The binding of the adatoms to the surface has a highly ionic character in the systems of the present experiment. An estimate is given for the screening length of the non-perfect conductor W(110):ks?1≈ 0.5 Å.  相似文献   

13.
The relaxation dynamics of matrix isolated CH and CD have been studied using laser-induced time and wavelength resolved spectroscopy. Vibrationally relaxed B(0′-0″) fluorescence occurs following laser excitation both above and below the gas phase dissociation limit. The vibrational relaxation rate in the B state of CH is found to be 4.6 × 106 sec?1 while the corresponding rate in CD is 5.7 × 105 sec?1. The primary accepting mode in the relaxation process is consistent with rotation.  相似文献   

14.
An expression for the calculation of 3d electronic band structures of metallic nickel is given in the tight-binding scheme using the extended Hu¨ckel method. An explicit formulation in the nearest neighbor approximation is given and the accuracy of the nearest neighbor approximation is discussed. It is found that when a combination of two Slater wave functions is used for each 3d orbital, and when overlap matrix elements between neighbors are included until convergence is achieved, the resulting 3d band structures and band width agree well with those obtained from ab initio tight-binding calculations. For nickel, this calculation gives a 3d band width of 2.48 eV, a degeneracy temperature of 2.8 × 103 K and a linear, low temperature electronic heat coefficient of 1.9 × 10?3 cal mol?1 deg?2.  相似文献   

15.
ZnO single crystals were doped with Mn and Co by diffusion. In the temperature range from 1400–1600 K the Mn and Co-diffusion-constants were determined:D Mn=3.2 · 10?3 exp (?2.87 eV/kT) cm2 sec?1 andD Co=1·10exp(?3.98 eV/kT) cm2 sec?1. The Mn doped ZnO crystals show a characteristic colour due to an absorption near the intrinsic absorption edge. The corresponding absorption spectra were measured forE⊥c andE∥c. A discussion of different absorption mechanism shows that a charge-transfer transition is responsible for this absorption.  相似文献   

16.
17.
Previous values of the pressure dependence of the magnetocrystalline anisotropy constant K1 of iron and nickel were revised. These values of K1?1 (dK1dp) depend on the magnetic field for iron, and do not for nickel. The value in iron extrapolated to infinitely strong magnetic field is ?7.8×10?6 bar?1 at room temperature and ?7.3×10?6 bar?1 at 77K, and in nickel at 15 KOe is ?7.5×10?6 bar?1 at room temperature and ?2.8×10?6 bar?1 at 77K.  相似文献   

18.
The time evolution of the KLL Auger spectrum of carbon as a function of temperature is used to derive the kinetics of the surface diffusion and bulk-to-surface precipitation of carbon on polycrystalline nickel. The results show that the activation energy for the surface diffusion of carbon atoms on polycrystalline nickel is 6.9 ± 0.6 kcalmole, and the activation energy for bulk-to-surface precipitation is 9.4 ± 0.6 kcalmole. The dependence on the surface diffusion coefficient Ds (cm2s?1), on the absolute temperature T can be represented, over the experimental temperature range, 350–425° C, by: ln Ds = 10.27 ? 3568T.  相似文献   

19.
Electron-phonon scattering rates in ultrapure single crystals of copper have been determined from the temperature dependence of the magnetoacoustic oscillation amplitudes for various orbits on the Fermi surface using both longitudinal and transverse waves. The central belly orbit seattering rate is found to be (6.0±0.3)×106 T 3 sec?1. Additionally, a rate of (2.9±0.2)×106 T 3 sec?1 is found which is attributed to belly orbits displaced from the zone center by about 1.25/a 0, wherea 0 is the lattice constant. Geometric oscillations associated with the [111]—directed open orbit are observed at low fields forq‖ [113] and the rate for this orbit is found to be (4.8±0.3)×106 T 3 sec?1. Geometric oscillations for the dog's bone and neck orbits are observable but rates for these orbits are believed to be unreliable. Our measured rates are compared with those of other workers.  相似文献   

20.
Measurements of both the absolute sticking probability near normal incidence and the coverage of H2 adsorbed on W(100) at ~ 300K have been made using a precision gas dosing system; a known fraction of the molecules entering the vacuum chamber struck the sample crystal before reaching a mass spectrometer detector. The initial sticking probability S0 for H2/W(100) is 0.51 ± 0.03; the hydrogen coverage extrapolated to S = 0 is 2.0 × 1015 atoms cm?2. The initial sticking probability S0 for D2/W(100) is 0.57 ± 0.03; the isotope effect for sticking probability is smaller than previously reported. Electron stimulated desorption (ESD) studies reveal that the low coverage β2 hydrogen state on W(100) yields H+ ions upon bombardment by 100 eV electrons; the ion desorption cross section is ~ 1.8 × 10?23 cm2. The H+ ion cross section at saturation hydrogen coverage when the β1 state is fully populated is ? 10?25 cm2. An isotope effect in electron stimulated desorption of H+ and D+ has been found. The H+ ion yield is ? 100 × greater than the D+ ion yield, in agreement with theory.  相似文献   

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