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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.
An analysis of the relationship between the EPR trigonal-field parameters and the local crystal structure of KZnF3:Fe3+system is presented by diagonalizing the complete energy matrices for a d5 configuration ion in a trigonal crystal field. We propose a two-layer-ligand model, in which the ligands consist of six nearest-neighbor F ions in the first layer and eight next nearest-neighbor K+ ions in the second layer. The calculation indicates that the local structure distortion of KZnF3:Fe3+system is due to the displacement of a K+ ion along C3 axis towards the Fe3+ ion, which leads to the shift of the F ions away from C3 axis. By simulating the EPR low-symmetry parameters D and (aF), the distorted angles between the Fe3+-F bonds and C3 axis are determined, Δθ1=2.58°, Δθ2=−1.4° at room temperature (300 K) and Δθ1=2.84°, Δθ2=−1.4° at low temperature (77 K). Those results are in good agreement with the experimental findings Δθ1=2.8±0.3°and Δθ2=−1.1±0.3°.  相似文献   

3.
The ligands 4,4,4-trifluoro-1-phenyl-1,3-butanedione (Hbfa) and 1,10-phenanthroline (phen) were used to prepare ternary lanthanide (Ln) complexes [Dy(bfa)3phen and Tm(bfa)3phen]. Crystal data: Dy(bfa)3phen C42H26F9N2O6Dy, triclinic, P1¯, a=9.9450(6) Å, b=14.0944(9) Å, c=14.6043(9) Å, α=82.104(1)°, β=87.006(1)°, γ=76.490(1)°, V=1971.1(2) Å3, Z=2; Tm(bfa)3phen C42H26F9N2O6Tm, triclinic, P1¯, a=9.898(5) Å, b=13.918(5) Å, c=14.753(5) Å, α=83.517(5)°, β=86.899(5)°, γ=76.818(5)°, V=1965.3(14) Å3, Z=2. The coordination number of the central Ln3+ (Ln=Dy, Tm) ion is eight, with six oxygen atoms from three Hbfa ligands and two nitrogen atoms from the phen ligand. The photophysical properties of the two complexes were studied by absorption spectra, diffuse reflectance spectra, and emission spectra. They show the characteristic luminescence of the corresponding Ln3+ ion in both visible and near-IR (NIR) region. Additionally, the energy transfer mechanisms between the ligands and central Ln3+ ions were discussed.  相似文献   

4.
Effective work functions (φ+ and φe) for positive-ionic and electronic emissions from polycrystalline metals of Nb, Mo, Ta, W and Ir are calculated according to our theoretical model by using those published data on both fractional surface area (Fi) and local work function (φi) of each metal surface composed of several patchy faces (1, 2, …, i). Comparison between the theoretical values thus obtained and those experimental data published to date yields the conclusions as follows. (1) With a slight error of less than ∼0.1 eV, the value of φe calculated with each of the metals is in fair or good agreement with that determined by experiment. (2) Such agreement is found also with φ+ for W. (3) In a typical case of W, where the degree of monocrystallization (δm) corresponding to the largest among the values of Fi is less than ∼0.5, the thermionic contrast (Δφ* ≡ φ+ − φe) is found again to be nearly equal to both theoretical and experimental values reported previously. (4) Each of the five metals shows that Δφ* at δm = 0.68-0.95 is smaller than Δφ* at δm < 0.5. (5) This result strongly supports our theoretical prediction that Δφ* decreases gradually to zero as δm increases beyond ∼0.5 up to ∼1. (6) Particularly, such a surface which has δm ≥ 0.96 exhibits Δφ* ≈ 0, apparently equivalent to the so-called “monocrystalline surface (δm = 1)”. These results lead to the conclusion that our theoretical model is valid for evaluating the effective work functions probably with a slight error of less than ∼0.1 eV, irrespective of both the surface species and the range of δm. In addition, our simple model makes it possible to analyze the mechanism of change in φ+ and φe according to the change in surface characters of both φi and Fi.  相似文献   

5.
Two novel complexes of Sm(III) and Dy(III) with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands were synthesized and their structure and luminescence properties were characterized. The complexes of [Ln(ODA)(phen)·4H2O]Cl·5H2O [Ln=Sm and Dy] crystallize in the monoclinic space group P21/n with Sm: a=12.3401(14) Å, b=16.821(2), c=12.6847(11) Å, β=107.939(10)°, V=2505.0(5) Å3, Z=4 and ρ=1.841 mg/m3, and with Dy: a=12.289(7) Å, b=16.805(6) Å, c=12.705(4) Å, β=108.144(18)°, V=2493.4(19) Å3, Z=4 and ρ=1.786 mg/m3. The complexes of [Sm(ODA)(phen)·4H2O]+ and [Dy(ODA)(phen)·4H2O]+ excited by UV light produce orange red and lightly white emissions, respectively, via the nonradiative energy transfer from phen to the metals. The quantum yield of the sensitized luminescence of [Dy(ODA)(phen)·4H2O]+ (Q=19%) is much greater than that of [Sm(ODA)(phen)·4H2O]+ (Q=1.4%). The luminescence decay times of the complexes were in a few microsecond range and independent of temperature.  相似文献   

6.
The isostructural polymeric compounds Co(thiazole)2X2 (X=Cl (1), Br(2)) have been synthesised by the addition of thiazole to an ethanolic solution of the corresponding anhydrous cobalt halide. Powder X-ray and neutron diffraction measurements were used for structural determination. The structures were determined using powder neutron diffraction data and Rietveld techniques: (1) C2/c, a=17.806(2) Å, b=3.6806(6) Å, c=14.807(3) Å, β=94.78(1)°, V=967.1(3) Å3, Z=4; (2) C2/c, a=18.079(3) Å, b=3.8138(8) Å, c=15.022(4) Å, β=92.71(1)°, V=1034.6(4) Å3, Z=4. Each linear polymer chain is composed of pseudo-octahedral, high-spin Co2+ centres, doubly linked by halide bridges. Magnetisation measurements of 1 and 2 at 5 K between 0 and 10 kG reveals a metamagnetic transition between antiferromagnetic and ferromagnetic states. Low temperature susceptibility data have been fitted to a one-dimensional Ising model with a mean field correction and were found to be anisotropic with ferromagnetic intrachain interactions along the b-axis and weaker antiferromagnetic interchain interactions.  相似文献   

7.
A theoretical method for studying the inter-relation between electron and molecule structure is proposed on the basis of the complete energy matrices of the electron-electron repulsion, the ligand-field and the spin-orbit coupling for d5 configuration ion in a trigonal ligand-field. As an application, the local distortion structure of (FeCl6)3- coordination complex for Fe3+ ions doped into CdCl2 is investigated. Both the second-order zero-field splitting parameter and fourth-order zero-field splitting parameter are considered simultaneously in the structural investigation. By diagonalizing the complete energy matrices, the local structure distortion parameters ΔR=−0.24 Å, Δθ=2.137° at 26 K and ΔR=−0.203 Å, Δθ=2.515° at 225 K for Fe3+ ions in CdCl2 are determined. These results elucidate a microscopic origin of various ligand-field parameters which are usually used empirically for the interpretation of electron paramagnetic resonance results. It is found that the theoretical results are in good agreement with the experimental values.  相似文献   

8.
From measurements of the decrease in the heat (enthalpy) of transition in the solid phase using differential scanning calorimetry, the apparent molar heats of solution, slope ΔHt/x, the partial molar heats of solution at infinite dilution, χ, and the heats of solution, ΔHs°, of Tl+ in CsNO3 crystal and Cs+ in TlNO3 crystal and Rb+ in CsNO3 crystal and Cs+ in RbNO3 crystal along with their recovered lattice energies, ΔHL°, are reported. ΔHs° of Tl+ and Rb+ in CsNO3 crystal are each found to be negligible or zero representing an ideal solid solution, i.e. ΔHmix=0. The complete phase diagrams of the TlNO3-CsNO3 and RbNO3-CsNO3 systems with details of the sub-solidus regions are included. The properties of Tl(1−x)CsxNO3 and Rb(1−x)CsxNO3 compositions are discussed in terms of a ‘mixed crystal’ or ‘crystalline solid solution’ in relation to parallel compositions of Tl(1−x)RbxNO3.  相似文献   

9.
State-of-the-art airborne lidar data of passive scalars have shown that the spatial stratification of the atmosphere is scaling: the vertical extent (Δz) of structures is typically ≈ΔxHz where Δx is the horizontal extent and Hz is a stratification exponent. Assuming horizontal isotropy, the volumes of the structures therefore vary as ΔxΔxΔxHzxDs where the “elliptical dimension” Ds characterizes the rate at which the volumes of typical non-intermittent structures vary with scale. Work on vertical cross-sections has shown that 2+Hz=2.55±0.02 (close to the theoretical prediction 23/9).In this paper we extend these (x, z) analyses to (z, t). In the absence of overall advection, the lifetime Δt of a structure of size Δx varies as ΔxHt with Ht=2/3 so that the overall space-time dimension is Dst=29/9=3.22…. However, horizontal and vertical advection lead to new exponents: we argue that the temporal stratification exponent Ht≈1 or ≈0.7 depending on the relative importance of horizontal versus vertical advection velocities. We empirically test these space-time predictions using vertical-time (z, t) cross-sections using passive scalar surrogates (aerosol backscatter ratios from lidar) at ∼3 m resolution in the vertical, 0.5-30 s in time and spanning 3-4 orders of magnitude in scale as well as new analyses of vertical (x, z) cross-sections (spanning over 3 orders of magnitude in both x, z directions). In order to test the theory for density fluctuations at arbitrary displacements in (Δz, Δt) and (Δx, Δz) spaces, we developed and applied a new Anisotropic Scaling Analysis Technique (ASAT) based on nonlinear coordinate transformations. Applying this and other analyses to data spanning more than 3 orders of magnitude of space-time scales we determined the anisotropic scaling of space-time finding the empirical value Dst=3.13±0.16. The analyses also show that both cirrus clouds and aerosols had very similar space-time scaling properties. We point out that this model is compatible with (nonlinear) “turbulence” waves, hence potentially explaining the observed atmospheric structures.  相似文献   

10.
To explore the possibility of K-level resolved, 2+1 resonance-enhanced multiphoton ionization (REMPI) processes of the methyl radical, the two-photon absorption selection rules and rotational line strengths of the 301 and 401 vibronic bands of the transition (n=3 or 4) were reported. Stringent selection rules, which were imposed upon these two-photon transitions, are the initial K″=3p (p=0,1,2,…), ΔK=±2, ΔU=±3, and ΔN=0,±1,±2 (O, P, Q, R, and S branches). The previously assigned 222 vibronic band of the methyl radical should be studied by the REMPI with a better spectral resolution and analyzed by the newly derived two-photon absorption selection rules and rotational line strength formulas.  相似文献   

11.
The microwave spectrum of 2-butynol, CH3CCCH2OH, has been investigated in the frequency range of 6-26.5 GHz. The spectra of the A and E torsional states were observed using Fourier transform microwave spectroscopy. Due to the presence of the cylindrically symmetric CC “spacer” between the methyl group and the rest of the molecule, the barrier to internal rotation, V3, is only 7 cm−1. One conformer of 2-butynol was observed and assigned. The spectrum was analyzed with the ρ-axis method using a very flexible Hamiltonian which gives a fit an order of magnitude better than that obtained with more standard code for internal rotation. The spectroscopic constants are: 23744.(18), 2093.429(1), 1966.358(1), and −400.34(2) MHz for A, B, C, and Dab; 0.48(1) kHz, −30.3(4) kHz, and 4.5(5) MHz for ΔJ, ΔJK, and ΔK; and 0.1406(6), 6.93(9) cm−1, −33.4(7) kHz, and 192.0(9) GHz for ρ, V3, LV, and F, respectively. The root mean squared error of the fit is 14 kHz. The angles between the internal rotor axis and principal axes are θa=12°, θb=78°, with θc held fixed at 90°.  相似文献   

12.
The complex perovskite solid solution (1−x) Pb(In1/2Nb1/2)O3-(x) Pb(Ni1/3Nb2/3)O3 has been successfully prepared by the Columbite precursor method. The temperature dependencies of the dielectric constant and pyroelectric coefficient were measured between −261 and 200 °C. Relaxor ferroelectric behavior has been noticed in all compositions across the solid solution. The room-temperature electrostrictive coefficient, Q33, was 1.83×10−2 C2/m4 for x=0.10. No room-temperature piezoelectric activity was detected; however, upon cooling to −261 °C the maximum coupling coefficients kp=29%, kt=11%, and k33=31% were observed for the composition x=1.00.  相似文献   

13.
The ν1 (A1, 1583.22 cm−1) and ν4 (E, 1615.33 cm−1) Si-D stretching bands of monoisotopic D3Si35Cl have been studied by FTIR spectroscopy with a resolution of 3.3×10−3 cm−1. We have assigned 2341 rovibrational lines for ν1 (Jmax=70, Kmax=19) and 6207 for ν4 (Jmax=75, Kmax=27). Both (ΔK=±1, Δ?=±1) and (ΔK=±2, Δ?=?1) interactions connect the v1=1 and v4=1 levels, the latter exerting moreover a weak ?(2, 2) interaction. These interactions were taken into account in a nonlinear least-squares fit, refining 29 free parameters with a standard deviation of 0.257×10−3 cm−1 over 6722 nonzero-weighted data. Blended lines and about 250 of the 330 lines belonging to the K=11 subband of ν1 and the KΔK=−6 subband of ν4 were zero-weighted because they are locally perturbed respectively by the neighboring upper states of the 2ν36 (E, 1561.95 cm−1) and 3ν3 (A1, 1604.81 cm−1) bands. Equivalent fits were obtained for altogether three different models obeying constraints according to the theory of unitary equivalent reductions of the rovibrational Hamiltonian. By means of a band contour simulation both the transition moment ratio |M1:M4|=0.67 and a positive sign of the Coriolis intensity perturbation were determined.  相似文献   

14.
Adsorption of carbon dioxide on a faujasite-type H-Y zeolite (Si:Al = 2.6:1) was studied by variable-temperature (200-290 K range) infrared spectroscopy. Adsorbed CO2 molecules interact with the Brønsted acid Si(OH)Al groups located inside the zeolite supercage, bringing about a characteristic bathochromic shift of the O-H stretching mode from 3645 cm−1 (free OH group) to 3540 cm−1 (hydrogen-bonded CO2 adsorption complex). Simultaneously, the asymmetric (ν3) mode of adsorbed CO2 is observed at 2353 cm−1. From the observed variation of the integrated intensity of the 3645 and 2353 cm−1 IR absorption bands upon changing temperature, corresponding values of standard adsorption enthalpy and entropy were found to be ΔH° = −28.5(±1) kJ mol−1 and ΔS° = −129(±10) J mol−1 K−1. Comparison with the reported values of ΔH° for CO2 adsorption on other zeolites is briefly discussed.  相似文献   

15.
Optical homodyne receivers based on modified balanced optical phase-locked loop is analyzed taking into account loop propagation delay. This modified loop contains all the components of a standard BOPLL in conjunction of an additional phase modulator. This modified loop offers a much improved tracking performance and also shows good improvements in the reduction performance over previously reported methods, like, relaxed line-width requirement and improved lock-in range. This study for the first time shows the imperfect-phase-recovery-induced power penalty as a function of laser line-width with the optimum phase deviations in the presence of non-negligible loop propagation delay. It is found that in order to maintain a 10−10 BER system performance with ξ = 1, R = 1 A/W, PR = −53 dBm, Δυ = 1 MHz, phase modulator sensitivity KPM = 10 rad/V and 10° phase deviation between the two transmitted bits, the loop delay must be kept below 3 ns. Further, the required line-width with the non-negligible loop delay time is evaluated and found to be (2.1 × 10−3)/τ, where τ (s) is the loop delay. This number corresponds to BER = 10−10, imperfect phase recovery power penalty of 1 dB and phase modulator sensitivity KPM = 20 rad/V.  相似文献   

16.
The 5d 26s 2 3 F 2 ground state of177Hf,179Hf and180Hf has been studied using the atomic beam magnetic resonance method. The atomic beam was produced by an universal evaporation technique described in a previous paper. The results are180Hfg j (3 F 2)=0.695812 (10)177Hf Δv(3 F 2;F=11/2?F=9/2)=991.7917 (10) MHz Δv(3 F 2;F=9/2?F=7/2)=477.0081 (10) MHz Δv(3 F 2;F=7/2?F=5/2)=162.8890 (10) MHz179HfΔv(3 F 2;F=13/2?F=11/2)=82.1320 (10) MHz Δv(3 F 2;F=11/2?F=9/2)=392.8498 (10) MHz. The magnetic dipole and electric quadrupole moments of the177Hf and179Hf nuclear ground states as calculated from these hyperfine structure measurements are the following: μ(177)=0.75(8)μ k , Q(177)=4.34 (65) barns μ(179)=?0.61 (6)μ k , Q(179)=4.90 (75) barns.  相似文献   

17.
We report an electron paramagnetic resonance (EPR) study at 33.9 GHz and room temperature of oriented single crystal samples of bis(l-asparaginato)Zn(II) doped with Cu(II). The variation of the spectra with magnetic field orientation was measured in three crystal planes (a*b, bc and a*c, with a*=b×c). These spectra display two groups of four peaks arising from the hyperfine interaction with the ICu=3/2 nuclear spins of copper. They were assigned to Cu(II) ions in two lattice sites related by a 180° rotation around the b-crystal axis. The g and hyperfine coupling (A) tensors of the Cu(II) ions were evaluated from the single crystal data. Some indeterminacy in the assignment of the signals was avoided measuring the EPR spectrum of a powder sample. Their principal values are g1=2.060(1), g2=2.068(2), g3=2.283(2), and A1≈0.1×10−4, A2=13×10−4 and A3=165×10−4 cm−1. The eigenvectors corresponding to g3 and A3 are coincident within the experimental error; the other eigenvectors are rotated 5.6° in the perpendicular plane. Considering the crystal structure of bis(l-asparaginato)Zn(II), our EPR results indicate that the Cu(II) impurities replace Zn(II) ions in the host crystal. We propose a molecular model based on the EPR data and the structural information, and analyse the results comparing the measured values with those obtained in similar systems.  相似文献   

18.
By analyzing the EPR spectrum of transition-metal ion Fe3+ in Al2O3:Fe3+ system, the local lattice structure around impurity Fe3+ ion in the crystal has been studied by means of the diagonalization of the energy matrices of the electron-electron repulsion, the ligand-field and the spin-orbit coupling for a d5 configuration ion in a trigonal ligand-field. Both the second-order and fourth-order EPR parameters D and (aF) are taken simultaneously in the structural investigation. The results indicate that the two three-edge-pyramids elongated obviously along C3 axis. The two distortion angles Δθ1=−1.1±0.1°,Δθ2=−1.8° as well as the two Fe-O bond lengths R1=2.016 A, R2=1.907 A are determined, respectively.  相似文献   

19.
Infrared spectra of PD3 have been measured in the 20-320 cm−1 range and in the region of the ν24 and ν13 fundamental bands near 750 and 1690 cm−1, respectively, with a resolution of ca. 0.0025 cm−1. Furthermore, submillimeter-wave spectra covering the J=4-3, 13-12, and 14-13 clusters in the vibrational ground state were recorded. The observed ΔJ=+1 rotational lines were augmented by about 5500 ground state combination differences formed from transitions belonging to the fundamental bands. Of these, 1300 involved perturbation-allowed lines with ΔK≠0. These data and observations taken from the literature were appropriately weighted and fitted to 14 ground state molecular constants. The A and B reductions of the rotational Hamiltonian were found to be equivalent. Improved effective ground state and equilibrium structures were determined for both PH3 and PD3; the equilibrium structures, re (PH)=141.1607(83) pm and αe (HPH)=93.4184(95)° and re (PD)=141.1785(57) pm and αe (DPD)=93.4252(68)°, are in good agreement.  相似文献   

20.
In the so-called ‘step-shape’ angular spin distribution model for layered systems, the non-collinear directions of the atomic magnetic moments are confined to the film plane and form a homogeneous fan spanning inside an (in-plane) angular interval Δφ centered at an angle φ0. A general approach for deriving the two parameters φ0 and Δφ via 57Fe Mössbauer spectroscopy measurements is discussed. The analysis extends our previously reported treatment, which assumed that the angular aperture Δφ develops symmetrically versus a fixed direction φ0 (e.g., the in-plane easy axis of magnetization) oriented either along or perpendicular to the in-plane projection of the Mössbauer γ-ray direction. The proposed approach is also applicable for those cases when not only the spin aperture Δφ is changing but also the aperture center φ0 is rotating under the influence of different external parameters, such as applied field, temperature, stress, etc. The method is suitable for applications to nanoscale layered heterostructures with in-plane uniaxial or unidirectional magnetic anisotropy. The method is applied to experimental data obtained on a 2-nm thick defected Fe layer with in-plane magnetic texture.  相似文献   

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