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1.
To elucidate the thermionic property of polycrystalline surfaces, a further study is made on the mean work functions (φ, φe and φ+) effective for negative-ionic, electronic and positive-ionic emissions. Comparison between theoretical analyses and experimental data yields the conclusions as follows. (1) The equation of φ = φe holds always with both mono- and polycrystalline surfaces. (2) The relation of φ = φe < φ+ applies to polycrystalline surfaces because they bear the thermionic contrast (Δφ* ≡ φ+ − φe > 0). (3) The value of Δφ* ranges from ∼0.4 to 0.9 eV depending upon the surface species of polycrystalline metals (e.g., W, Re and Pt), whilst Δφ* = 0 for monocrystalline surfaces. (4) When the degree of monocrystallization (δm) is less than ∼50%, the theoretical value of Δφ* is virtually independent of δm and agrees well with experimental data, nearly the same within ±0.1 eV among the so-called “polycrystalline” surfaces of W. (5) As δm increases beyond ∼80 up to 100%, Δφ* decreases rapidly down to 0 eV, showing again a good agreement between theory and experiment. (6) Our theoretical model is valid in evaluating the effective mean work functions, irrespective of the range of δm.  相似文献   

2.
For better understanding the peculiarities of work function, a simple model is devised to calculate the effective work functions (?+ and ?e) for positive-ionic and electronic emissions from polycrystalline surfaces, which have a work function range from the maximum (?max) to the minimum (?min). Analysis of the theoretical results thus obtained and also of experimental data published to date enables us to find the quantitative relation between the thermionic contrast (Δ?* ≡ ?+ − ?e) and the degree of monocrystallization (δm), thereby yielding the three formulae of (1) Δ?* = c for 0 < δm ? 1/2 (polycrystal), (2) Δ?* = 4 m (1 − δm) for l/2 ? δm ? 1 (polycrystal), and (3) Δ?* = 0 for δm = 1 (monocrystal). For a given surface consisting of a number of patchy faces (i), δm corresponds to the largest among its fractional surface areas (Fi) having different values of local work function (?i). In a typical case of tungsten, the constant of c is evaluated theoretically to be 0.53 ± 0.09 eV, which well agrees with 0.59 ± 0.06 eV determined experimentally by many workers and also which satisfies the essential condition of Δ?* ≦ c < ?max − ?min ≈ 0.8-1.0 eV. Our theoretical model is quite simple, but it is very useful for (1) evaluating both ?+ and ?e with an uncertainty of less than ±0.1 eV, (2) finding the quantitative relation between Δ?* and δm for actual surfaces of both poly- and monocrystals, and also (3) getting a substantial clue as to the problem how the effective work functions are governed by the surface characteristics of both Fi and ?i.  相似文献   

3.
Thermo-optical parameters of CdSe/ZnS core-shell nanoparticles suspended in toluene were measured using a thermal lens (TL) technique. TL transient measurements were performed using the mode-mismatched dual-beam (excitation and probe) configuration. A He-Ne laser at λp = 632.8 nm was used as the probe beam and an Ar+ laser (at λe = 514.5 nm) was used as the excitation beam for studies as a function of both core size and concentration of CdSe/ZnS nanocrystals. The fraction thermal load (φ) and radiative quantum efficiencies (η) of the CdSe/ZnS were determined. Dependence on core size (∼2-5 nm) and concentration (∼0.01-0.62 mg/ml) was observed for both φ and η parameters.  相似文献   

4.
The secondary ion mass spectrum of silicon sputtered by high energy C60+ ions in sputter equilibrium is found to be dominated by Si clusters and we report the relative yields of Sim+ (1 ≤ m ≤ 15) and various SimCn+ clusters (1 ≤ m ≤ 11 for n = 1; 1 ≤ m ≤ 6 for n = 2; 1 ≤ m ≤ 4 for n = 3). The yields of Sim+ clusters up to Si7+ are significant (between 0.1 and 0.6 of the Si+ yield) with even numbered clusters Si4+ and Si6+ having the highest probability of formation. The abundances of cluster ions between Si8+ and Si11+ are still significant (>1% relative to Si+) but drop by a factor of ∼100 between Si11+ and Si13+. The probability of formation of clusters Si13+-Si15+ is approximately constant at ∼5 × 10−4 relative to Si+ and rising a little for Si15+, but clusters beyond Si15 are not detected (Sim≥16+/Si+ < 1 × 10−4). The probability of formation of Sim+ and SimCn+ clusters depends only very weakly on the C60+ primary ion energy between 13.5 keV and 37.5 keV. The behaviour of Sim+ and SimCn+ cluster ions was also investigated for impacts onto a fresh Si surface to study the effects that saturation of the surface with C60+ in reaching sputter equilibrium may have had on the measured abundances. By comparison, there are very minor amounts of pure Sim+ clusters produced during C60+ sputtering of silica (SiO2) and various silicate minerals. The abundances for clusters heavier than Si2+ are very small compared to the case where Si is the target.The data reported here suggest that Sim+ and SimCn+ cluster abundances may be consistent in a qualitative way with theoretical modelling by others which predicts each carbon atom to bind with 3-4 Si atoms in the sample. This experimental data may now be used to improve theoretical modelling.  相似文献   

5.
S. Ogawa 《Surface science》2007,601(18):3838-3842
Ultraviolet photoelectron spectroscopy was used to measure the oxygen uptake, changes in work function due to the surface dipole layer of adsorbed-oxygen atoms, Δ?SDL, and changes in band bending due to the defect-related midgap state, ΔBB, simultaneously during oxidation on Si(0 0 1) surface at room-temperature, RT, under an O2 pressure of 1.3 × 10−5 Pa. The oxygen dosage dependence of Δ?SDL revealed that dissociatively adsorbed-oxygen atoms occupy preferentially dimer backbond sites at the initial stage of Langmuir-type adsorption, which is associated with a rapid increase of ΔBB. When raising temperature to ∼600 °C, such preferential occupation of the dimer backbond sites by oxygen atoms is less significant and ΔBB becomes smaller in magnitude. The observed relation between Δ?SDL and ΔBB indicates that point defects (emitted Si atoms + vacancies) are more frequently generated by oxygen atoms diffusing to the dimer backbond sites at lower temperature in RT −600 °C.  相似文献   

6.
The large-amplitude bending motion in CsOH, a ‘classical’ molecule whose microwave spectrum was first recorded in 1967, has been studied ab initio. The three-dimensional potential energy surface has been calculated at the RCCSD(T)_DK3/[QZP + g ANO-RCC (Cs, O, H)] level of theory and employed in MORBID calculations of the rotation-vibration energies and intensities. The ground electronic state is 1Σ+ with the equilibrium structure re(Cs-O) = 2.3930 Å, re(O-H) = 0.9587 Å, and ∠e(Cs-O-H) = 180.0°. The O-H moiety is bound to Cs by an ionic bond and the molecule can be described as Csδ+(OH)δ-. Hence, the bending potential is shallow and gives rise to large-amplitude bending motion. The ro-vibrationally averaged structural parameters, determined as expectation values over MORBID wavefunctions, are 〈r(Cs-O)〉0 = 2.3987 Å, 〈r(O-H)〉0 = 0.9754 Å, and 〈∠(Cs-O-H)〉0 = 163°. Although the averaged structure in the vibrational ground state is far from being linear, the Yamada-Winnewissi-linearity parameter for CsOH is γ0≈-1.0, the value characteristic for a linear molecule.  相似文献   

7.
The pure rotational spectrum of ZnO has been measured in its ground X1Σ+ and excited a3Πi states using direct-absorption methods in the frequency range 239-514 GHz. This molecule was synthesized by reacting zinc vapor, generated in a Broida-type oven, with N2O under DC discharge conditions. In the X1Σ+ state, five to eight rotational transitions were recorded for each of the five isotopologues of this species (64ZnO, 66ZnO, 67ZnO, 68ZnO, and 70ZnO) in the ground and several vibrational states (v = 1-4). Transitions for three isotopologues (64ZnO, 66ZnO, and 68ZnO) were measured in the a3Πi state for the v = 0 level, as well as from the v = 1 state of the main isotopologue. All three spin-orbit components were observed in the a3Πi state, each exhibiting splittings due to lambda-doubling. Rotational constants were determined for the X1Σ+ state of zinc oxide. The a3Πi state data were fit with a Hund’s case (a) Hamiltonian, and rotational, spin-orbit, spin-spin, and lambda-doubling constants were established. Equilibrium parameters were also determined for both states. The equilibrium bond length determined for ZnO in the X1Σ+ state is 1.7047 Å, and it increases to 1.8436 Å for the a excited state, consistent with a change from a π4 to a π3σ1 configuration. The estimated vibrational constants of ωe ∼ 738 and 562 cm−1 for the ground and a state agreed well with prior theoretical and experimental investigations; however, the estimated dissociation energy of 2.02 eV for the a3Πi state is significantly higher than previous predictions. The lambda-doubling constants suggest a low-lying 3Σ state.  相似文献   

8.
The emission spectra of CaH and CaD have been recorded at high resolution using a Fourier transform spectrometer and bands belonging to the E2Π-X2Σ+ transition have been measured in the 20 100-20 700 cm−1 region. A rotational analysis of 0-0 and 1-1 bands of both the isotopologues has been carried out. The present measurements have been combined with the previously available pure rotation and vibration-rotation data to provide improved spectroscopic constants for the E2Π state. The constants ΔG(½) = 1199.8867(34) cm−1, Be = 4.345032(49) cm−1, αe = 0.122115(92) cm−1, re = 1.986633(11) Å for CaH, and ΔG(½)=868.7438(46) cm−1, Be = 2.212496(51) cm−1, αe = 0.036509(97) cm−1, re = 1.993396(23) Å for CaD have been determined.  相似文献   

9.
High-pressure resistivity and X-ray diffraction measurements were conducted on La0.85MnO3−δ at ∼6 and ∼7 GPa, respectively. At low pressures the metal-insulator transition temperature (TMI) increases linearly up to a critical pressure, P* ∼3.4 GPa, followed by reduction in TMI at higher pressure. Analysis of the bond distances and bond angles reveals that a bandwidth increase drives the increase in TMI below P*. The reduction in TMI at higher pressures is found to result from Jahn-Teller distortions of the MnO6 octahedra. The role of anharmonic interatomic potentials is discussed.  相似文献   

10.
An initial stage of oxidation of a cesium-covered Ni (1 1 0) surface has been studied by metastable-induced electron spectroscopy (MIES) and low-energy electron diffraction (LEED). The MIES brought spectra with Cs 6s induced peak (P6s), Cs 5p (P5p), O 2p induced peak (Pox) and a structure related to the substrate Ni 3d states (P3d). The work function change Δφ showed an oscillatory behavior in the progress of surface oxidation. The process is divided into three stages: (i) at low O2 exposures, Δφ > 0 with unchanging P5p and P6s; (ii) at moderate exposures, Δφ < 0 with a drastic decrease in the P6s intensity; (iii) at higher exposures, Δφ > 0 with shifts of peaks P5p and Pox to higher energies, together with an appearance of peak P3d. A three-step model of initial oxidation of alkali-covered Ni (1 1 0) surfaces is presented.  相似文献   

11.
Herein, a discussion of the effect of deposition temperature on the magnetic behavior of Ni0.5Zn0.5Fe2O4 thin films. The thin films were grown by r.f. sputtering technique on (1 0 0) MgO single-crystal substrates at deposition temperatures ranging between 400 and 800 °C. The grain boundary microstructure was analyzed via atomic force microscopy (AFM). AFM images show that grain size (φ∼70-112 nm) increases with increasing deposition temperature, according to a diffusion growth model. From magneto-optical Kerr effect (MOKE) measurements at room temperature, coercive fields, Hc, between 37and 131 Oe were measured. The coercive field, Hc, as a function of grain size, reaches a maximum value of 131 Oe for φ ∼93 nm, while the relative saturation magnetization exhibits a minimum value at this grain size. The behaviors observed were interpreted as the existence of a critical size for the transition from single- to multi-domain regime. The saturation magnetization (21 emu/g<Ms<60 emu/g) was employed to quantify the critical magnetic intergranular correlation length (Lc≈166 nm), where a single-grain to coupled-grain behavior transition occurs. Experimental hysteresis loops were fitted by the Jiles-Atherton model (JAM). The value of the k-parameter of the JAM fitted by means of this model (k/μo∼50 A m2) was correlated to the domain size from the behavior of k, we observed a maximum in the density of defects for the sample with φ∼93 nm.  相似文献   

12.
The pure rotational spectrum of ZnS (X1Σ+) has been measured using direct-absorption millimeter/sub-millimeter techniques in the frequency range 372-471 GHz. This study is the first spectroscopic investigation of this molecule. Spectra originating in four zinc isotopologues (64ZnS, 66ZnS, 68ZnS, and 67ZnS) were recorded in natural abundance in the ground vibrational state, and data from the v = 1 state were also measured for the two most abundant zinc species. Spectroscopic constants have been subsequently determined, and equilibrium parameters have been estimated. The equilibrium bond length was calculated to be re ∼ 2.0464 Å, which agrees well with theoretical predictions. In contrast, the dissociation energy of D∼ 3.12 eV calculated for ZnS, assuming a Morse potential, was significantly higher than past experimental and theoretical estimates, suggesting diabatic interaction with other potentials that lower the effective dissociation energy. Although ZnS is isovalent with ZnO, there appear to be subtle differences in bonding between the two species, as suggested by their respective force constants and bond length trends in the 3d series.  相似文献   

13.
We report an ab initio calculation, at the MR-SDCI + Q + Erel/[Roos ANO (Fe), aug-cc-pVQZ (C, N)] level of theory, of the potential energy surface for 6Δi FeNC. From the ab initio results, we have computed values for the standard spectroscopic parameters of FeN12C and FeN13C. Analytical representations of the potential energy surfaces have been fitted through the ab initio points, and the resulting functions have been used for directly solving the rotation-vibration Schrödinger equation by means of the MORBID program and by means of an adiabatic-separation method. For 6Δi FeNC, our ab initio calculations show that the equilibrium structure is linear with re (Fe-N) = 1.9354 Å and re (N-C) = 1.1823 Å. We find that the bending potential is very shallow, and the MORBID calculations show that the zero-point averaged structure is bent with the expectation values 〈r (Fe-N)〉 = 1.9672 Å, 〈r(N-C)〉 = 1.1866 Å, and . The experimentally derived bond length r0 (N-C) = 1.03(8) Å reported for 6Δi FeNC by Lie and Dagdigian [J. Chem. Phys. 114 (2001) 2137-2143] is much shorter than the corresponding ab initio re-value and the averaged value from MORBID. Our calculations suggest that this discrepancy is caused by the inadequate treatment of the large-amplitude bending motion of 6Δi FeNC. It would appear that for floppy triatomic molecules such as FeNC, r0-values have little physical meaning, at least when they are determined with the effects of the large-amplitude bending motion being ignored, i.e., under the assumption that the r0 structure is linear.  相似文献   

14.
The pure rotational transitions of HN2+ and DN2+ in the first excited vibrational states for all the fundamental vibrational modes have been observed in the range of 300-750 GHz. The molecular constants determined are much more accurate compared with those obtained from the infrared spectroscopy. The equilibrium rotational constants, Be = 46832.45 (71) MHz for HN2+ and Be = 38708.38 (58) MHz for DN2+, have been determined by correcting for the higher-order vibration-rotation interaction effects, γij, obtained by an infrared investigation. The equilibrium bond lengths are derived from these equilibrium rotational constants: re(H-N) = 1.03460 (14) Å and re (N-N) = 1.092698 (26) Å.  相似文献   

15.
Results of step fluctuation experiments for Mo(0 1 1), using low-energy electron microscopy, are re-examined using recently developed procedures that offer accurate coefficients of surface mass diffusion. By these means, surface diffusion Ds is documented at T/Tm ∼ 0.5, while the crossover to relaxation driven by bulk vacancy diffusion is inferred for T/Tm ∼ 0.6. Here, Tm is the melting temperature Tm = 2896 K. We obtain Ds = 4 × 10−4 exp(−1.13 eV/kBT) cm2/s for the temperature interval 1080-1680 K. Possible indications of diffusion along step edges appear for T/Tm ∼ 0.4. The same measurements of step fluctuation amplitudes determine also the step stiffness, which by symmetry is anisotropic on Mo(0 1 1). It is shown that three independent procedures yield mutually consistent step stiffness anisotropies. These are (1) step fluctuation amplitudes; (2) step relaxation rate anisotropies; and (3) the observed anisotropies of islands in equilibrium on the Mo(0 1 1) surface. The magnitude of the step stiffness obtained from step edge relaxation is consistent with earlier measurements that determine diffusion from grain boundary grooving.  相似文献   

16.
We report a successful fabrication of c-axis oriented GdBa2Cu3O7−δ (GdBCO) films on the BaSnO3 (BSO) buffer layers on ion-beam assisted deposition (IBAD)-MgO template by pulsed-laser deposition (PLD). The (0 0 l) growth and in-plane textures of BSO buffer layers were found sensitive to the substrate temperature (Ts). With increasing the BSO layer thickness up to ∼165 nm, in-plane texture (Δ? ∼ 6.2°) of BSO layers was almost unaltered while completely c-axis oriented BSO layers were obtainable from samples with the thickness below ∼45 nm. On the BSO buffer layers showing in-plane texture of 6.2° and RMS surface roughness of ∼8.6 nm, GdBCO films were deposited at 780–800 °C. All GdBCO films exhibited Δ? values of 4.6–4.7°, Tc,zero of ∼91 K, and critical current density (Jc) over 1 MA/cm2 at 77 K in a self-field. The highest Jc value of 1.82 MA/cm2 (Ic of 51 A/cm-width) was achieved from the GdBCO film deposited at Ts of 790 °C. These results support that BSO can be a promising buffer layer on the IBAD-MgO template for obtaining high-Jc GdBCO coated conductors.  相似文献   

17.
Charoite is a hydrous alkali calcium silicate mineral [K4NaCa7Ba0.75Mn0.2Fe0.05(Si6O15)2(Si2O7)Si4O9(OH)·3(H2O)] exhibiting an intense lilac colour related to Mn2+ and Fe3+ colour centres. These ions also contribute to a strong luminescence at ∼585 and 705 nm. This work studies the thermal dependence of these luminescent centres by (i) thermoluminescence (TL) of pre-heated and pre-irradiated charoite aliquots, (ii) by time-resolved cathodoluminescence (TRS-CL) at room and cryogenic temperatures (RT and CT), (iii) by spatially resolved spectra CL under scanning electron microscopy (SRS-CL-SEM) and (iv) by ion beam spectra luminescence (IBL) with H+, H2+ and 4He+ ions at RT and LT. The main peak, ∼585 nm, is linked to a transition 4T1,2 (G)→6A7(S) in Mn2+ ions in distorted six-fold coordination and the emission at ∼705 nm with Fe2+→Fe3+ oxidation in Si4+ lattice sites. Less intense UV-blue emissions at 340 and 390 nm show multi-order kinetic TL glow curves involving continuous processes of electron trapping and de-trapping along with an irreversible phase transition of charoite by de-hydroxylation and lattice shortening of Δa=0.219 Å, Δb=0.182 Å; Δc=0.739 Å. The Si-O stressed lattice of charoite has non-bridging oxygen or silicon vacancy-hole centres, and Si-O bonding defects which seem to be responsible for the 340 nm emission. Extrinsic defects such as the alkali (or hydrogen)—compensated [AlO4/M+] centres could be linked with the 390 nm emission. Large variations in 585 and 705 nm intensities are strongly temperature dependent, modifying local Fe-O and Mn-O bond distances, short-range-order luminescence centres being very resistant under the action of the heavy ion beam of 4He+. The SRS-CL demonstrates strong spatial heterogeneity in the luminescence of the charoite.  相似文献   

18.
The electronic structure and the spectroscopic constants of the low lying electronic states of the NaK+ ionic molecule have been determined through using an ab initio approach involving a non-empirical pseudopotential for the Na and K cores and core valence correlation correction. The potential energy of nearly 26 electronic states of 2Σ+, 2Π, and 2Δ symmetries has been calculated up to their dissociation limit Na(4d) + K+ and Na+ + K(6s). Their spectroscopic constants (Re, De, Te, ωe, ωeχe, and Be) are derived and compared with the few available theoretical studies. A good agreement has been found for the ground state and few excited states with previous works. New potential energy curves were presented, for the first time, for the higher excited states. Numerous avoided crossing between electronic states of 2Σ+, 2Π symmetries have been localized and analyzed. Their existences are related to the charge transfer between the two ionic molecules Na+K and NaK+. Furthermore, we have determined the transition dipole moments for several states and analyzed the avoided crossings related to charge transfer between alkaline atoms.  相似文献   

19.
Six types of BiFeO3 ceramic samples, with subtle differences in synthesis conditions, were prepared. The comparison of their phases, electrical resistivity, and porosity revealed that the use of Bi2O3 and Fe2O3 powders of <1 μm size and a rapid liquid-phase sintering process of 855 °C for 5 min at 100 °C/s is beneficial to synthesize poreless single-phase BiFeO3 samples with high electrical resistivity of ∼5×1012 Ω cm. Deoxygenated BixFeyO1.5x+1.5yδ (xy, δ≥0) impurities were identified and found to be the main cause of low electrical resistivity and high porosity in the multi-phase samples. Large saturation polarization of 16.6 μC/cm2 and low leakage current density of 30 mA/m2, both at a high electric field of 145 kV/cm, were measured in the optimized single-phase samples at room temperature besides a large piezoelectric d33 coefficient of 27 pC/N and an obvious canted antiferromagnetic behavior.  相似文献   

20.
We calculated and studied the quantum coherence effects of a degenerate transition Fg = 3 ↔ Fe = 2 system interacting with a weak linearly polarized (with σ± components) probe light and a strong linearly polarized (with σ± components) coupling field. Due to the competition between the drive Rabi frequency and the Zeeman splitting, electromagnetically induced transparency (EIT) and electromagnetically induced absorption (EIA) are appeared at the different values of applied magnetic field in both cases that the Zeeman splitting of excited state Δe is smaller than the Zeeman splitting of ground state Δg (i.e., Δe < Δg) and Δe > Δg. It is shown that the resonance is broader and contrasts are higher for Δe < Δg than that for Δe > Δg at the same Rabi frequencies of probe and coupling fields.  相似文献   

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