Spin Hamiltonian of 51V2+ in MgO, as Derived from Electron Nuclear Double Resonance

1968 ◽  
Vol 49 (7) ◽  
pp. 2971-2973 ◽  
Author(s):  
H. W. de Wijn ◽  
A. H. M. Schrama

The electron nuclear double resonance spectrum of both isotopes 151 Eu and 163 Eu has been measured in a single crystal of calcium fluoride containing about 0.01 % Eu 2+ . As the lines were narrow ( ~ 10kc/s) the hyperfine structure parameter and the nuclear g-value were measured to high precision giving the following values: A 151 = -102.9069±0.0013 Mc/s, A 153 = -45.6730±0.0025 Mc/s B 151 = -0.7855±0.0052 Mc/s, B 153 = -2.0294 ±0.0068 Mc/s, gI 151 = - 7.4969±0.0020 (x 10 -4 )β, gI 153 = - 3.3125±0.0030 (x 10 -4 )β. In order to fit the measured line positions to the spin Hamiltonian which is usually assumed for the system it was necessary to add small higher-order terms. The results of these measurements are compared with the precise atomic beam measurement on Eu.


1976 ◽  
Vol 54 (2) ◽  
pp. 217-222 ◽  
Author(s):  
K. Pack ◽  
A. Manoogian

The electron-nuclear double resonance (ENDOR) of 53Cr3+ ions and the electron spin resonance (ESR) of VO2+ ions are studied in single crystals of AlCl3∙6H2O. The ENDOR measurements are done at 4.2 K while the resonance of VO2+ is studied at room temperature. The sign of the Cr3+ spin Hamiltonian zero field splitting parameter D is found to be negative while the anisotropic hyperfine parameter has the relation A < B. It is concluded that the octahedron of waters surrounding the chromium ion is trigonally compressed. The value of the 53Cr3+ quadrupole interaction parameter Q′ is nearly the same as that found previously in the cesium alums even though the D value is considerably smaller in AlCl3∙6H2O. This indicates that Q′ is independent of D at 4.2 K in these salts and the expected proportionality [Formula: see text], which is based on a purely static distortion for the octahedron of waters surrounding the Cr3+ ion, does not hold. The resonance results for VO2+ show the nature of the two inequivalent but otherwise similar Al∙6H2O complexes in the unit cell. The VO2+∙5H2O complexes associated with the two types of aluminum sites are found to be rotated relative to each other by an angle of 33 ± 3° in the plane perpendicular to the crystal c axis. A comparison of the spin Hamiltonian parameters of VO2+ and 53Cr3+ in AlCl3∙6H2O with those obtained previously in CsAl alum indicates that the Al∙6H2O complexes in CsAl alum are more susceptible to distortion upon impurity doping than are those in AlCl3∙6H2O.


1981 ◽  
Vol 59 (2) ◽  
pp. 298-304 ◽  
Author(s):  
M. E. Ziaei

An electron nuclear double resonance investigation of CsCdF3:M (M = Mn2+, Ni2+, Cr3+, and Co2+) has been carried out to measure the transferred hyperfine interaction (thfi) between M and nearest neighbour fluorine ions. A general spin Hamiltonian which takes account of the multiplicity of the interacting nuclei, is solved for a general orientation of the magnetic field. An example is given to show that theory agrees well with experiment. Spin transfer parameters obtained are of similar order of magnitude for the same ions in similar host lattices.


Electron nuclear double resonance has been carried out in single crystals of MgO containing Co 2± . An accurate check of the spin-Hamiltonian has been made and the relevant parameters measured as A = 290.55 ± 0.06 Mc/s, g' N β N /gβ = 2.34 ± 0.02 x 10 -4 .


In view of the limitations of the usual spin-Hamiltonian for characterizing exactly the low-lying levels of the paramagnetic ions in crystals, as evident from some recent electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) experiments on iron-transition group and rare-earth ions, a method is described here for deducing a general spin-Hamiltonian determined exclusively by the crystal-field symmetry. The Hamiltonian thus derived obviously includes all possible independent spin-operators, and, in general, has more terms than those considered in the usual spin-Hamiltonian. The method has been applied to the case of cubic crystalline symmetry, and the spin-Hamiltonian is written out correctly for the Zeeman field (H) independent part and the linearly field-dependent part, for all ions with both electron spin S and nuclear spin I up to 2. Terms which are quadratic in H are considered for spin values S and I up to 1 only. Relative importance of the independent operators are discussed with particular reference to two cases: Co 2+ in eight co-ordinated cubic compounds and Yb 3+ in CaF 2 , which are expected to be two extreme examples of the effect of the excited levels on the ground state. Some of the terms which are usually neglected in the usual spin-Hamiltonian are shown to make significant contributions to the spin-levels. The importance of the terms quadratic in Zeeman field is emphasized for precise ENDOR experiments.


1996 ◽  
Vol 442 ◽  
Author(s):  
J.-M. Spaeth ◽  
S. Greulich-Weber ◽  
M. März ◽  
E. N. Kalabukhova ◽  
S. N. Lukin

AbstractThe electronic structure of nitrogen donors in 6H-, 4H- and 3C-SiC is investigated by measuring the nitrogen hyperfine (hf) interactions with electron nuclear double resonance (ENDOR) and the temperature dependence of the hf split electron paramagnetic resonance (EPR) spectra. Superhyperfine (shf) interactions with many shells of 13C and 29Si were measured in 6H-SiC. The hf and shf interactions are discussed in the framework of effective mass theory. The temperature dependence is explained with the thermal occupation of the lowest valley-orbit split A1 and E states. It is proposed that the EPR spectra of P donors observed previously in neutron transmuted 6H-SiC at low temperature (<10K) and high temperature (>60K) are all due to substitutional P donors on the two quasi-cubic and hexagonal Si sites, whereby at low temperature the E state is occupied and at high temperature the A1 state. The low temperature spectra are thus thought not to be due to P-vacancy pair defects as proposed previously.


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