Hyperfine structure of EPR spectra of Gd3+ odd isotopes in PbMoO4, Pb5Ge3O11, YVO4, and quadrupole interaction (temperature dependence)

A hyperfine structure of EPR signals of odd isotopes Gd³⁺ in Pb₅Ge₃O₁₁, PbMoO₄, and YVO₄ single crystals has been investigated at different temperatures. The observation of forbidden (with the nuclear spin flip) transitions has made it possible to determine quadrupole interaction P ₂ ⁰ associated with the gradient of the electric field of ligands at the impurity. It has been shown for the first time that, under the condition |P ₂ ⁰ | ≥ |A _{x, y} | (A _i are the tensor components), not only the magnitudes of splitting but also the observed asymmetry in a hyperfine structure (in perpendicular orientations of the magnetic field) depends on mutual signs of parameters of initial splitting b ₂ ⁰ and P ₂ ⁰ . Results of studying the spectra have demonstrated that |b ₂ ⁰ (T)|/|P ₂ ⁰ (T)| ～ const for a concrete single crystal, which assumes the similarity of physical mechanisms determining these parameters.     

Estimation of higher-order magnetic spin interactions of Fe(III) and Gd(III) ions doped in α-alumina powder with multifrequency EPR

Fe(III) and Gd(III) ions in α-alumina (A1₂O₃) exhibit spin states ofS = 5/2 andS = 7/2 respectively. The magnitude of the zero-field interaction (ZFI) (D = 0.10?0.15 cm^?1) gives rise to an inter Kramers doublet splitting in the same order of magnitude as the X-band electron paramagnetic resonance (EPR) quantum (0.3 cm^?1). It is demonstrated that through a careful step-by-step analysis and spectral simulation of EPR spectra taken at D-band (130 GHz), Q-band (35 GHz), and X-band (9 GHz) at room temperature, the (relative) sign and magnitude of the ZFI parameters, b ₂ ⁰ , b ₄ ⁰ , and b ₄ ³ , can be reliably estimated.     

Parametrization of two-body perturbation on atomic fine and hyperfine structure. The configuration (6p)3 in the bismuth atom

A method of simultaneous parametrization of one- and two-body interactions on atomic hyperfine structure of configurationl ^N is proposed and applied for the analysis of the configuration (6p)³ in the bismuth atom. For this purpose, the hyperfine structure splittings of the levels²D ₃ ^2/0 ,²D ₅ ^2/0 and²P ₁ ^2/0 were measured. The finally obtained values of HFS parameters are: for one-body parameters (in MHz):a _p ⁰¹ =2,537(9),a _p ¹² =5,182 (12),a′¹⁰=?2,019(10),b _p ⁰² =?3,198(53),b _p ¹¹ =2,816(54); for two-body parameters (in MHz):x _pp ^′/01 ,₂=284(3),x _pp ^′/12 ,₂=581(5),x _pf ^′/12 ,₂=170(70),x _pp ^′/02 ,₂=?359(36),x _pf ^′/02 ,₂=?33(100). The value of the quadrupole moment of the nucleus ₈₃ ²⁰⁹ Bi is also discussed.     

Hyperfeinanomalie im151Eu und153Eu

Using the Mössbauer effect, the ratios of theg factors and the hyperfine splitting constants for the 21.6 keV state and the ground state in¹⁵¹Eu and of the 103 keV state and the ground state in¹⁵³Eu have been measured. From these results values for the hyperfine anomaly of⁰Δ ₁₅₁ ²² =?0.81(8)% and⁰Δ ₁₅₃ ¹⁰³ =+ 1.8(8)% have been derived for¹⁵¹Eu and¹⁵³Eu, respectively.     

Paramagnetische Resonanz des dreiwertigen Gadoliniums in YPO4, YVO4 und YAsO4

The EPR spectra of Gd³⁺-doped isostructural single crystals of YPO₄, YVO₄, and YAsO₄ have been measured in X-band at room temperature and at nitrogen and helium temperatures. The zero-field splitting can be described by the five crystal-field parametersb ₂ ⁰ ,b ₄ ⁰ ,b _6/0,b ₄ ⁴ , and b ₆ ⁴ fitted to a tetragonal spin-Hamiltonian corresponding to the point symmetry D_2d of the Gd³⁺ site. The values ofg and b ₂ ⁰ vary significantly with host lattice and with temperature.     

Temperature dependence of the ground state splitting of Mn2+ in some scheelite type crystals

The EPR spectrum of Mn²⁺ in CaMoO₄, CdMoO₄, CaWO₄ and SrWO₄ has been investigated in the temperature range from 4.2–380 K. Results are given for the Spin-Hamiltonian parametersb ₂ ⁰ andb ₄ ⁰ . They are completed by data forb ₂ ⁰ of Mn²⁺ in SrMoO₄ [1] and discussed with respect to resonant vibrations.     

Fourth-order zero-field splitting parameters of [Mn(cyclam)Br2]Br determined by single-crystal W-band EPR

Single-crystal W-band (95 GHz) electron paramagnetic resonance (EPR) studies have been performed at 20 K and at room temperature on a tetragonal Mn(III) compound with potential application as a building block for high-spin clusters. The observed EPR spectra correspond to an anisotropic high-spinS = 2 ground state and have been attributed to equivalent centers related by four-fold symmetry. Accurate values for the spin Hamiltonian parameters were obtained from the analysis of the data at both temperatures. At 20 K the contribution of fourth-order zero-field splitting terms was shown to be significant, with parameter values B ₄ ⁰ = 0.0009(3) cm^?1, B ₄ ² = 0.0006(2) cm^?1 and B ₄ ⁴ = 0.0017(3) cm^?1, to be considered together with the second-order parametersD = ?1.1677(7) cm^?1 andE= ?0.0135(6) cm^?1.     

Heterogeneity in the Nitroxide Micro-Environment: Polarity and Proticity Effects in Spin-Labeled Proteins Studied by Multi-Frequency EPR

This study aims to investigate the g _xx heterogeneity of the g-tensor commonly observed in high-field electron paramagnetic resonance (EPR) spectra of nitroxide spin-labeled sites in proteins. This heterogeneity is addressed in terms of spin-label populations characterized by different polarity and H-bonding properties of the nitroxide micro-environment. The g _xx value for each population is determined from the fit of continuous-wave high-field spectra obtained at 95, 275 and 360 GHz with a series of nitroxide spin-labels covalently attached to different sites in both membrane and water-soluble proteins. The spin-labeled proteins investigated include sensory rhodopsin II and its cognate transducer molecule (HtrII) from Natronomonas pharaonis both in micelles and membranes, bacteriorhodopsin from Halobacterium salinarum in native purple membrane lipid bilayers and water-soluble colicin A from Escherichia coli. To avoid contributions to the g _xx spectral features of the nitroxide label due to nuclear quadrupole interactions arising from ¹⁴N nuclei, and to simplify the nitrogen hyperfine pattern, methanethiosulfonate spin labels, containing the ¹⁵N isotope (I = 1/2) in some experiments, were employed. A consistent analysis of all multi-frequency EPR spectra revealed three distinct g _xx values, g _xx ⁱ , for each investigated position of the labeled proteins. In contrast, distinctly different nitrogen hyperfine splittings A _zz of the nitroxides in the various labeled proteins could not be resolved, but rather an average hyperfine splitting $\bar{A}_{{zz}}$ was obtained. The g _xx ⁱ values as well as the fractions of the different nitroxide populations were found to be correlated with the average hyperfine constant $\bar{A}_{{zz}},$ a parameter which likewise is known to be sensitive to the local polarity of the spin-label micro-environment. Plotting the different g _xx ⁱ values obtained for each EPR spectrum versus $\bar{A}_{{zz}}$ of the labeled proteins reveals new interesting aspects of the nitroxide label micro-environment in terms of polarity and H-bonding propensity (proticity). Linear approximations of the different regions of the plot g _xx ⁱ versus $\bar{A}_{{zz}}$ are presented and compared with theoretical and experimental data available from the literature.     

Effect of hydrostatic pressure and temperature on the EPR spectrum of the Mn2+ ion in Zn(BF4)2 · 6H2O

A study of the effect of hydrostatic pressure and temperature on the EPR spectrum of the Mn²⁺ ion in Zn(BF₄)₂ · 6H₂O is reported. The break in the temperature dependence of the b ₂ ⁰ parameter at 196 K is evidence of the existence of a phase transition accompanied by a change in the thermal expansion coefficient. It is shown that pressure considerably affects the spectral parameters by reducing the axial parameter b ₂ ⁰ and increasing the cubic one, b ₄ ⁰ . At 9 kbar, the b ₂ ⁰ parameter is temperature independent. A comparison of the pressure dependences of the spectra of Zn(BF₄)₂ · 6H₂O, ZnSiF₆ · 6H₂O, ZnTiF₆ · 6H₂O, and MgSiF₂ · 6H₂O crystals suggests equal hydrogen-bond lengths in these compounds. A ligand hyperfine structure has been detected, which originates from the Zeeman interaction with the proton nuclei surrounding Mn²⁺ and manifests itself in the formation of satellites at each EPR line, their separation being proportional to the magnetic field. The nonlinear pressure dependence of the linewidth is related to the structural features of the crystal under study.     

Pulse ENDOR studies on the radical pair P 700 +· A 1 ·− and the photoaccumulated quinone acceptor A 1 ·− of photosystem I

The secondary acceptor A₁ of the electron transport chain(s) of photosystem (PS) I is a phylloquinone (vitamin K₁, VK₁). Pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments at X-band frequencies were performed on the photoaccumulated acceptor radical A ₁ ^·? and the radical pair state P ₇₀₀ ^·+ A ₁ ^·? in PS I ofThermosynechococcus elongatus. The data obtained were compared with data from the respective radical anion of VK₁ in organic solvents. The unusualg tensor magnitude of A ₁ ^·? is explained by the hydrophobic binding pocket of this radical. The hyperfine couplings and the spin (and charge) density distribution is very different for A ₁ ^.? in PS I and VK ₁ ^·? in frozen alcoholic solution. This is attributed to a rather strong one-sided hydrogen bond to A ₁ ^·? . The presence of a hydrogen bond to A ₁ ^·? has only a minor effect ong. The hyperfine coupling constants of A ₁ ^·? determined from the radical pair spectra deviate only slightly from those derived from photoaccumulated A ₁ ^·? in PS I treated with dithionite at high pH. ENDOR resonances of the proton in a H bond were detected and an estimate of the strength and geometry of this bond to A ₁ ^·? was obtained. The significance of the hydrogen bond and other (hydrophobic) interactions of A₁ with the surrounding are briefly discussed.     

High-frequency EPR studies on cofactor radicals in photosystem I

Electron paramagnetic resonance (EPR) spectroscopy at W-band (94 GHz) is used to resolve theg-tensors of the radical ions of the primary chlorophyll donor P ₇₀₀ ^+? and the quinone acceptor A ₁ ^?? in photosystem I. The obtainedg-tensor principal values are compared with those of the isolated pigment radicals in organic solvents and the shifts are related to an impact of the protein environment. P ₇₀₀ ^+? has been investigated in photosystem I single crystals at 94 GHz. W-band EPR applied to the photoinduced radical pair P ₇₀₀ ^+? A ₁ ^?? is used to correctly assign theg-tensor axes of P ₇₀₀ ^+? to the molecular structure of the primary donor. Density functional theory calculations on a model of A ₁ ^?? in its binding pocket derived from the recent crystal structure of photosystem I were utilized to correlate experimental magnetic resonance parameters with structural elements of the protein.     

The primary and secondary acceptors in bacterial photosynthesis III. Characterization of the quinone radicals Q A − ⋅ and Q B − ⋅ by EPR and ENDOR

Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) techniques were used to investigate the electronic structure of the primary (Q _A ^?? ) and secondary (Q _B ^?? ) ubiquinone electron acceptors in reaction centers (RCs) of the photosynthetic bacteriumRhodobacter sphaeroides. To reduce the EPR linewidth, the high-spin Fe²⁺ present in native RCs was replaced by diamagnetic Zn²⁺. Experiments were performed both on frozen solutions and single crystals at microwave frequencies of 9, 35 and 94 GHz. Differences in the EPR/ENDOR spectra were observed for Q _A ^?? and Q _B ^?? , which are attributed to different environments of the quinones in the RC. The differences exhibited themselves in: (i) the g-tensors, (ii) the¹⁷O and¹³C hyperfine coupling (hfc) constants of the quinones labeled at the carbonyl group, (iii) the¹H-hfcs of the quinone ring and (iv) the exchangeable protons hydrogen bonded to the carbonyl oxygens. From these results and from H/D exchange experiments, the following conclusions were drawn: both Q _A ^?? and Q _B ^?? have at least two hydrogen bonds of different strengths to the carbonyl oxygens. The hydrogen bonds for Q _A ^?? are stronger and more asymmetric than for Q _B ^?? . For Q _A ^?? the stronger bond (to O₄) was assigned to His(M219) and the weaker (to O₁) to Ala(M260). For Q _B ^?? the stronger bond (to O₄) was assigned to His(L190), with several weaker bonds (to O₁) to Ser(L223), Ile(224) and Gly(L225). From the temperature dependence of the hfcs of the exchangeable protons some dynamic properties of the RC were deduced. Hfcs with more distant nitrogens were observed by electron spin echo envelope modulation (ESEEM). For Q _A ^?? they were assigned to N_δ of His(M219) and to the peptide backbone nitrogen of Ala(M260) and for Q _B ^?? to N_δ of His(L190). These interactions indicate the extent of the electron wave function, which is important for the understanding of the electron transfer mechanism. Based on the magnetic resonance results, the function of the quinone acceptors in the reaction center is discussed.     

Nuclear structure and the hyperfine interaction of oriented152Eu,155Eu,and153Gd in gold

Nuclear orientation of^152,155Eu and¹⁵³Gd in Gold has been used to determine the nuclear magnetic moment of¹⁵⁵Eu, (μ¹⁵⁵Eu)=1.93±0.26 n.m., and several mixing ratios of γ and β^? transitions in the decays. The hyperfine field of dilute EuAu alloys was found to beH _hf=134±10 kOe and for GdAu, |μH| was found to be in the range 0 to 1.0×10⁵ Oe·n.m.     

The decay of the Bethe-Salpeter kernel inP(ϕ)2 quantum field models

We extend methods of high temperature expansions to show that for even weakly coupledP(?)₂ quantum field models the Bethe-Salpeter kernel has 4 particle decay. More precisely ifK denotes the Euclidean Bethe-Salpeter kernel $$|K(x_1 ,x_2 ,x_3 ,x_4 )| \leqq Oe^{ - m_0 (1 - \varepsilon )d_2 } ,$$ wherex=(x ⁰,x ¹),d ₂=2|x ₁ ⁰ +x ₂ ⁰ ?x ₃ ⁰ ?x ₄ ⁰ |+|x ₁ ⁰ ?x ₂ ⁰ |+|x ₃ ⁰ ?x ₄ ⁰ | and ε(λ)→0 as λ→0. Our methods apply to otherr particle irreducible kernels.     

Theoretical investigation of Q A −· -ligand interactions in bacterial reaction centers ofRhodobacter sphaeroides

Density functional theory was used to calculate magnetic resonance parameters for the primary stable electron acceptor anion radical (Q _A ^?· ) in its binding site in the bacterial reaction center (bRC) ofRhodobacter sphaeroides. The models used for the calculations of the Q _A ^?· binding pocket included all short-range interactions of the ubiquinone with the protein surroundings in a gradual manner and thus allowed a decomposition and detailed analysis of the different specific interactions. Comparison of the obtained hyperfine and quadrupole couplings with experimental data demonstrates the feasibility and reliability of calculations on such complex biologically relevant systems. With these results, the interpretation of previously published 3-pulse electron spin echo envelope modulation data could be extended and an assignment of the observed double quantum peak to a specific amino acid is proposed. The computations provide evidence for a slightly altered binding site geometry for the Q_A ground state as investigated by X-ray crystallography with respect to the Q _A ^t-· anion radical state as accessible via EPR spectroscopy. This new geometry leads to improved fits of the W-band correlated-coupled radical pair spectra of Q _A ^?· -P ₈₆₅ ^+· compared to orientation data from the crystal structure. Finally, a correlation of the¹⁴N quadrupole parameters of His219 with the hydrogen bond geometry and a comparison with previous systematic studies on the influence of hydrogen bond geometry on quadrupole coupling parameters (J. Fritscher: Phys. Chem. Chem. Phys. 6, 4950–4956, 2004) is presented.     

Electronic properties of charged fullerenes characterized by EPR and Vis-NIR spectroscopy

EPR and Vis-NIR absorption spectra have both been measured for clarification of contradictory statements about the para-and diamagnetic states of fullerenes. Thereby identification of one sharp EPR signal in solution at room temperature to C ₆₀ ^? (g=2.000±4.0001; ΔB=0.07±0.01 mT) could be made upon using different fullerene sources (TechnoCarbo, Hoechst) and methods of anion generation (chemically, electrochemically, and photochemically). This fact is also supported by the similar observation for a monosubstituted derivative (g=1.9999; ΔB=0.10 mT), in which a small broadening of this sharp signal is found originating from additional¹H hyperfine interactions. Furthermore theg-values of the radical anions of C₆₀ increase with charge (g(C ₆₀ ^? <g(C ₆₀ ^2? ) < <g(C ₆₀ ^3? ) <g(C ₆₀ ^5? )) indicating largest contributions from spin-orbit coupling for the monoanion. No diamagnetic states for the dianions of [60]- and [70]- fullerenes could be found so far but biradical species with largest zero field splittingsD=2.7 mT (C ₆₀ ^2? ), andD=3.1 mT (C ₇₀ ^2? ), respectively. The cation formation of C₆₀ (g=2.0023-2.0029; ΔB=0.15-0.20 mT) with antimony pentachloride was controlled by mass spectrometry. Stable cations were found only in methylenechloride. In other solvents like toluene addition reactions seem to occur.     

EPR investigations of SiC and SiOC nanometric powders

EPR investigations are performed in SiC and SiOC nanometric powders annealed between 1200 and 1800°C. By using different EPR frequency bands and a suitable spectra analysis, three quite different paramagnetic defects with well defined $\tilde g_i $ (i=1, 2, 3) and hyperfine $\tilde A_i $ (i=1, 2) tensors account for the EPR signal in these materials. The defects are characterized by $\tilde g_1 $ (g ₁ ^‖ =2.0046(3), g ₁ ^? =2.0023(3)), $\tilde g_2 $ (g ₂ ^‖ =2.0037(3), g ₂ ^? =2.0028(3)) and isotropic $\tilde g_3 $ (2.0030(3)) tensors. In SiC powders, the defects assignment is discussed with respect to the different SiC forms, namely α-SiC and β-SiC polytypes as well as amorphous SiC and carbon present in minor concentration in the network. In SiOC powders, the above defects are evidenced only at high annealing temperature (T _a≥1200°C) when the oxygen contained is highly reduced.     

EPR of carbonate derived radicals: Applications in dosimetry, dating and detection of irradiated food

After exposure of biological (tooth enamel, bone, …) and synthetic apatites to ionizing radiation, the so-called “asymmetric EPR signal nearg = 2” is formed. Although this signal is being used in EPR dosimetry, dating and detection of irradiated food for many years already, its composite character and the precise nature of the radicals contributing to the spectrum are still insufficiently known and/or recognized. For some fifteen years already, the EPR group in Ghent is gaining extensive experience on the radicals present in calcified tissues and model systems like synthetic apatites, calcites and single crystals doped with carbonate. It will be shown that the majority of radicals in calcified tissues are carbonate derived, e.g., CO ₂ ^? , CO ₃ ^? , CO ₃ ^3? while also phosphate derived radicals like PO ₄ ^2? and oxygen species (O^?, O ₃ ^? ) have been identified with EPR and/or ENDOR. For the EPR applications mentioned above, the most important type of radicals is CO ₂ ^t- (g values ranging from 2.0035 to 1.9970). A second type of radicals which is very intriguing but still badly known, exhibits a spectrum atg values around 2.0045. It is very apparent in tooth enamel below doses of 1 Gy, it has been observed in certain fossil teeth in a very prominent way and also in irradiated food containing bone (e.g., frog legs). It will be shown that the organic origin of this signal can be questioned. The importance of other radicals like CO ₃ ^3t- and CO ₃ ^t- for EPR applications will also be discussed.     

Hyperfine structure of the atomic osmium spectrum: Superposition of configurations and the effect of nucleus volume

The contributions of the superposition of configurations ns ²5d ⁷6s+ns5d ⁷6sn′s+ns5d ⁷6s ² (n=1–5, n′=7–10) to the parameters of the hyperfine structure a _5d ⁰¹ , a _5d ¹² , a _5d ¹⁰ , a _6s ¹⁰ in the spectrum of the osmium atom Os I are calculated. Nonzero contributions are shown to be made only to the parameters a _5d ¹⁰ and a _6s ¹⁰ . This fact justifies the inclusion of the parameter a _5d ¹⁰ in the semiempirical analysis of experimental values of magnetic dipole constants of the hyperfine structure of the 5d ⁷ s configuration in the spectrum of the osmium atom. The effect of nucleus volume on the parameters of the hyperfine structure in the spectra of osmium isotopes ¹⁸⁷Os and ¹⁸⁹Os is estimated.