THE SPIN HAMILTONIAN AND INTENSITIES OF THE ESR SPECTRA ORIGINATING FROM LARGE ZERO-FIELD EFFECTS ON 6S STATES

1966 ◽  
Vol 44 (3) ◽  
pp. 503-508 ◽  
Author(s):  
F. Holuj
Keyword(s):  
Energy Levels ◽  
Esr Spectra ◽  
Zero Field ◽  
Spin Hamiltonian ◽  
Crystalline Field ◽  
Field Effects

By considering the Zeeman term small in relation to crystalline field terms of the spin Hamiltonian,[Formula: see text]an expression for transitions between the energy levels of the resulting Kramers doublets has been derived. Graphs of the resulting parameters are presented as functions of the crystalline field. The relative intensities of transitions are also considered fully.

ESR STUDY OF SPIN-HAMILTONIAN PARAMETERS AND CRYSTAL FIELD ENERGY LEVELS FOR THE LOW C3 SYMMETRY Fe3+ CENTER IN GREEN SAPPHIRE CRYSTALS AND POWDER

2007 ◽  
Vol 21 (04) ◽  
pp. 225-236 ◽  
Author(s):  
P. LIMSUWAN ◽  
N. UDOMKAN ◽  
P. WINOTAI
Keyword(s):  
Rotation Angle ◽  
Energy Levels ◽  
Heat Treating ◽  
Esr Spectra ◽  
Field Energy ◽  
Hamiltonian Matrix ◽  
Magnetic Field Direction ◽  
Spin Hamiltonian ◽  
Corundum Structure ◽  
Hamiltonian Parameters

In this report, Fe 3+ impurity ions present in green sapphire ( Al 2 O 3) were studied experimentally, by heating a light green sapphire in flowing oxygen atmosphere for 12 h from 1200, 1300, 1400, 1500 and 1600°C, respectively. Electron spin resonance (ESR) spectra in X-band (~9.45 GHz ) were recorded by mounting the crystal with the c-axis perpendicular (θ = 90°) to the magnetic field direction. The spectra were recorded and simulated by a numerical diagonalization of spin Hamiltonian matrix in the range from 0 to 180 degrees for every 15 degrees of rotation angle (φ). In our case, only the last two sets of peaks strongly depend on the rotation angle (φ), and each exhibits C 3 symmetry due to two magnetically inequivalent Fe 3+ sites in the corundum structure. For polycrystalline ESR spectra, seven main Fe 3+ ESR absorption peaks occur at the resonance magnetic fields of 100.20, 310.24, 486.80, 525.00, 550.60, 761.00 and 777.00 mT respectively. Specifically, ESR signals show that the number of paramagnetic Fe 3+ ions increase roughly linearly with the heat treating temperature, having the [Formula: see text] ratio ~1.41 at 1600°C.

scholarly journals EPR of Compound I: An Illustrated Revision of the Theoretical Model

2020 ◽  
Vol 51 (11) ◽  
pp. 1559-1589
Author(s):  
Maruan Bracci ◽  
Sabine Van Doorslaer ◽  
Inés García-Rubio
Keyword(s):  
Free Radical ◽  
Energy Levels ◽  
Magnetic Interaction ◽  
Local Environment ◽  
Paramagnetic Species ◽  
Zero Field ◽  
Spin Hamiltonian ◽  
Compound I ◽  
Zero Field Splitting ◽  
Counter Rotation

AbstractCompound I has been postulated to be the reactive species in many heme catalysts, which performs different chemistry and shows different properties in different enzymes. The aim of this review is to present a comprehensive model which has been successfully used to interpret the EPR spectra of various Compound I species. The theoretical approach established by seminal articles will be revisited and its ability to explain experimental results will be illustrated by simulating selected spectra from the literature. Compound I stores two oxidizing equivalents, one in the paramagnetic iron(IV)-oxo moiety, and another one as a free radical on the porphyrin ligand or an amino acid in the protein. To describe the interactions of the two paramagnetic species with each other and with their local environment, the spin Hamiltonian of the system is built step by step. The Fe(IV) center is described using a two-hole model. The effect of the crystal-field and spin–orbit coupling on the energy levels is calculated with this simple approach, which allows to obtain spin Hamiltonian parameters like zero-field splitting and effective g-values for the iron. The magnetic interaction between the Fe(IV) center and the free radical is considered and allowed to vary in sign (ferromagnetic to antiferromagnetic) and magnitude to interpret the EPR of Compound I species in different systems. Since orbital overlap is crucial for exchange interaction, special emphasis is made in obtaining the orientation of Fe semi-occupied orbitals by extending the counter-rotation concept, which relates the directions of magnetic, electronic, and molecular axes.

ESR SPECTRA OF Fe+3 IN SINGLE CRYSTALS OF ANDALUSITE

1966 ◽  
Vol 44 (3) ◽  
pp. 509-523 ◽  
Author(s):  
F. Holuj ◽  
J. R. Thyer ◽  
N. E. Hedgecock
Keyword(s):  
Single Crystals ◽  
Room Temperature ◽  
Esr Spectra ◽  
Zero Field ◽  
Spin Hamiltonian ◽  
Zero Field Splitting ◽  
Field Splitting ◽  
K Band

ESR spectra of Fe+3 in andalusite have been investigated at X- and K-band frequencies at room temperature. They have been interpreted on the assumption that Fe+3 occupies the two inequivalent Al+3 sites in andalusite. The spectra show large zero-field splitting. The constants of the conventional orthorhombic spin Hamiltonian which fit the spectra are as follows: for site I: b20 = 15.0 ± 0.1 kG, b22 = 5.0 ± 0.1 kG, and isotropic g = 2.001 ± 0.002; for site II: b20 = 20.1 ± 0.1 kG, b22 = 0.075 ± 0.010 kG, and isotropic g = 2.004 ± 0.0005. A study of the intensities of ESR signals due to site I follow a pattern predicted by theory. The implications of these results are considered briefly.

ELECTRON SPIN RESONANCE OF Fe+3 IN CORDIERITE

1966 ◽  
Vol 44 (11) ◽  
pp. 2749-2755 ◽  
Author(s):  
N. E. Hedgecock ◽  
S. C. Chakravartty
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Room Temperature ◽  
Esr Spectra ◽  
Orthorhombic Symmetry ◽  
Zero Field ◽  
Spin Hamiltonian ◽  
Zero Field Splitting ◽  
Field Splitting ◽  
Spin Resonance

ESR spectra of Fe+3 located at one of the aluminium sites in cordierite have been investigated at X- and K-band frequencies at room temperature. The spectra exhibit large zero-field splitting and have been fitted to a spin Hamiltonian of orthorhombic symmetry, having constants b20 = 14.6 ± 0.1 kG, b22 = 8.5 ± 0.1 kG, and isotropic g = 2.004 ± 0.002.

Spin-disorder resistivity and crystalline field effects inTmH2

1986 ◽  
Vol 34 (7) ◽  
pp. 4782-4785 ◽  
Author(s):  
J. P. Burger ◽  
J. N. Daou ◽  
A. Lucasson ◽  
P. Vajda
Keyword(s):  
Crystalline Field ◽  
Field Effects ◽  
Spin Disorder

scholarly journals The principal magnetic susceptibilities of neodymium sulphate octahydrate at low temperatures

1939 ◽  
Vol 170 (941) ◽  
pp. 266-271 ◽  
Keyword(s):  
Low Temperatures ◽  
Room Temperature ◽  
Energy Levels ◽  
Constant Factor ◽  
The Other ◽  
Crystalline Field ◽  
Cubic Symmetry ◽  
The Subject ◽  
The Difference ◽  
The One

The magnetic and other related properties of neodymium sulphate have been the subject of numerous investigations in recent years, but there is still a remarkable conflict of evidence on all the essential points. The two available determinations of the susceptibility of the powdered salt at low temperatures, those of Gorter and de Haas (1931) from 290 to 14° K and of Selwood (1933) from 343 to 83° K both fit the expression X ( T + 45) = constant over the range of temperature common to both, but the constants are not the same and the susceptibilities at room temperature differ by 11%. The fact that the two sets of results can be converted the one into the other by multiplying throughout by a constant factor suggested that the difference in the observed susceptibilities was due to some error of calibration. It could, however, also be due to the different purity of the samples examined though the explanation of the occurrence of the constant factor is then by no means obvious. From their analysis of the absorption spectrum of crystals of neodymium sulphate octahydrate Spedding and others (1937) conclude that the crystalline field around the Nd+++ ion is predominantly cubic in character since they find three energy levels at 0, 77 and 260 cm. -1 .* Calculations of the susceptibility from these levels reproduce Selwood’s value at room temperature but give no agreement with the observations-at other temperatures. On the other hand, Penney and Schlapp (1932) have shown that Gorter and de Haas’s results fit well on the curve calculated for a crystalline field of cubic symmetry and such a strength that the resultant three levels lie at 0, 238 and 834 cm. -1 , an overall spacing almost three times as great as Spedding’s.

Ab initio predictions of the zero field splittings and the singlet–triplet transition strengths for the n → π* transition of selenoformaldehyde

1993 ◽  
Vol 71 (10) ◽  
pp. 1706-1712 ◽  
Author(s):  
D.C. Moule ◽  
L. Chantranupong ◽  
R.H. Judge ◽  
D.J. Clouthier
Keyword(s):  
Energy Levels ◽  
Random Phase ◽  
Open Shell ◽  
Oscillator Strengths ◽  
Basis Set ◽  
Zero Field ◽  
Zero Field Splitting ◽  
Hartree Fock ◽  
Lower Valence ◽  
Polarization Functions

The energy levels of the lower valence and Rydberg states of selenoformaldehyde, CH2Se, have been calculated by the SCF/CI method. Wavefunctions for the ROHF (restricted open shell Hartree–Fock) states were obtained with the Binnings–Curtis double-ζ basis set, augmented with Rydberg and polarization functions. Configuration interaction was applied to the parent configurations, PCMO (parent configuration molecular orbital). Oscillator strengths were evaluated for the allowed electric dipole transitions by the RPA (random phase approximation), and SOPPA (second-order polarization propagator approximation) methods. The spin-orbit contribution to the zero field splitting of the first triplet state, 3A2(n,π*) as well as the oscillator strengths to the three spin components were calculated by perturbation theory. These calculations predict that the Sx, Sy, and Sz components are shifted by −96.091,−96.707, and + 29.167 cm−1, respectively, from their unperturbed position. The oscillator strengths for the three components fx, fy, and fz of the 3A2(n,π*) ← 1A1(g.s.) transition were calculated to be 3.45 × 10−7, 1.15 × 10−7, and 173.0 × 10−7.

Theoretical Investigations Of The Spin Hamiltonian Parameters Of Zrsio4:Np4+

2004 ◽  
Vol 59 (7-8) ◽  
pp. 471-475
Author(s):  
Shao-Yi Wu ◽  
Hui-Ning Dong
Keyword(s):  
Experimental Data ◽  
Energy Levels ◽  
Structural Data ◽  
Superposition Model ◽  
Spin Hamiltonian ◽  
Theoretical Investigations ◽  
Structure Constants ◽  
Crystal Field Parameters ◽  
Hamiltonian Parameters ◽  
Theoretical Results

In this work, the spin Hamiltonian (SH) parameters g|| and g⊥, and the hyperfine structure constants A|| and A⊥ for ZrSiO4:Np4+ are investigated on the basis of the perturbation formulas of these parameters for a 5f3 ion in tetragonal (D2d) symmetry. In these formulas, the contributions to the SH parameters from the second-order perturbation terms, the admixtures of various energy levels and the covalency effect are taken into account. The related crystal-field parameters are calculated from the superposition model and the local structural data of the Zr4+ site occupied by the impurity Np4+. The calculated SH parameters agree reasonably with the experimental data. The validity of the theoretical results is discussed.

Local Symmetry and Crystalline Field Effects in Charge-Ordered Yb4As3

2000 ◽  
Vol 69 (11) ◽  
pp. 3633-3641 ◽  
Author(s):  
Osamu Sakai ◽  
Masahumi Kohgi ◽  
Hiroyuki Shiba ◽  
Akira Ochiai ◽  
Hidekazu Aoki ◽  
...  
Keyword(s):  
Local Symmetry ◽  
Crystalline Field ◽  
Field Effects
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