Light polarization in iodine-doped polyvinyl alcohol films

¹²⁹I Mössbauer measurements have been performed on unidirectionally stretched iodinedoped polyvinyl alcohol(PVA) films which are widely used as optical polarizers. In the films iodine is observed to be in the form of I^?, I ₃ ^? , and I ₅ ^? and the stretch of the films increases the abundance of the polyiodides, I ₃ ^? and I ₅ ^? . In the stretched PVA films, it has become clear that the linear polyiodides lie parallel to the stretching direction.     

Chemical structure of iodine-doped polyisoprene

A nonconjugated conducting polymer (1,4-rans-polyisoprene) at different iodine doping levels has been studied with the 27.7-keV Mössbauer resonance of¹²⁹I. At the light doping level, almost all iodines are covalently bonding to the carbon atoms, breaking the double bonds of the main chain. At the medium doping level, other iodine species are found, which are idendified as anion species, l^?, l ₃ ^? and l ₃ ^? .At the heavy doping level, polyiodide anions, l ₃ ^? and l ₅ ^? , increase as compared to the covalently bonding iodine atoms and addtionally molecular iodine l₂ exists.     

Studying track electrons in frozen aqueous solutions by means of emission Mössbauer spectroscopy

It is shown by means of emission Mössbauer spectroscopy that the reactivity of NO ₃ ^? cations with quasi-free track electrons exceeds those of H₃O⁺, ClO ₄ ^? , and HSO ₄ ^? ions by a factor of only three. This is in drastic contradiction to published assertions that these values differ by two orders of magnitude. An explanation for this discrepancy is proposed.     

Cation distribution of the system Zn1−xCoxFeMnO4 by x-ray,electrical conductivity and Mössbauer studies

Structural, electrical and Mössbauer studies were carried out for the system Zn_1?xCo _x Fe MnO₄. It is observed that forx?0.6, the ionic configuration of the system is Zn _1?x ²⁺ Mn _x ²⁺ [Co _x ³⁺ Mn _1?x ³⁺ Fe³⁺]O ₄ ^2? and forx?0.8 Fe³⁺ ions occupy tetrahedral site also. On the basis of electrical and Mössbauer studies a probable valence distribution of CoMnFeO₄ has been suggested. All the compounds showed positive values of thermoelectric coefficient and electrical conduction takes place by a hopping mechanism. Activation energy and thermoelectric coefficient values decreased with decrease in concentration of Zn²⁺ ions. The compounds possess low mobility values varying between 10^?7 and 10^?9 cm²/V sec.     

Determination of theL-shell conversion coefficient for the 26 keV Mössbauer transition in161Dy

TheL-shell conversion coefficient of the 26 keV Mössbauer transition in¹⁶¹Dy has been determined to be α_L=2.4 _?0.2 ^+0.3 by coincidence techniques using high resolution Ge(Li) and Si(Li) detectors. With theoretical values for theM- andN-shells the total conversion coefficient is calculated to be α_tot=2.9 _?0.2 ^+0.3 .     

Mössbauer study of Hungarian phlogopites

Ultramafic xenoliths of mantle origin occur in Hungarian Cretaceous lamprophyres. The aim of the present work was to determine the iron positions and their occupancy in phlogopites originated from ultramafic xenoliths by the help of Mössbauer spectroscopy. On the basis of the evaluation of the Mössbauer spectra Fe _M1 ²⁺ , Fe _M2 ²⁺ , Fe _M2 ³⁺ and Fe _M1 ³⁺ (or in some cases Fe_tet) octahedral and tetrahedral iron sites were identified in the samples. Quantitative analysis was performed for all of the iron sites. We have observed large differences between the Fe²⁺/Fe³⁺ ratio in samples originated from 120–150 km deepness, which phlogopites having been existed at different erosion circumstances. We have found a significantly higher Fe²⁺/Fe³⁺ ratio in phlogopites which had been solidified in 120–150 km depth from the surface of Earth 70–100 million years ago, than those had been crystallized in 60–80 km deepness.     

Emission Mössbauer spectroscopic studies of57Fe atoms produced in57Co-labelled trinuclear cobalt-iron halogenoacetate complexes

Mixed-valence states of⁵⁷Fe atoms produced after EC-decay of⁵⁷Co in a series of trinuclear cobalt-iron halogenoacetate complexes, [Co^IIFe ₂ ^III O(CH_3?nX_nCO₂)₆(H₂O)₃] (0≤n≤3, X=Cl, Br, and I), were studied by comparing the results obtained by emission Mössbauer spectroscopy with those observed in absorption Mössbauer spectra of analogous trinuclear iron complexes, [Fe^IIFe ₂ ^III O(CH_3?nX_nCO₂)₆(H₂O)₃]. Some of the emission Mössbauer spectra show a temperature-dependent mixed-valence state as found in the absorption Mössbauer spectra. Others show a somewhat different temperature dependence compared with the absorption Mössbauer spectra. The results were interpreted in terms of after-effects of the EC-decay.     

Incomplete magnetic ordering in Fe2(1−y)Mg1+y Ti y O4 spinels with intermediate compositiony

Static magnetization measurements on the ferrimagnetic spinels Fe_2(1?y)Mg_1+y Ti _y O₄ withy=0.3, 0.4, 0.5, and 0.6 show that these compounds have no well-defined orderdisorder transition temperature and that their ferrimagnetism may not be described in terms of the Néel theory. From the Mössbauer spectra we conclude that a temperature dependent number of the ferric ions does not participate in the ferrimagnetism of those compounds with compositiony≧0.4. The explanation of the observed magnetic and Mössbauer properties is based on the assumption that each ferric ion must have at least two magnetic linkages of the type Fe _A ³⁺ ?O^2??Fe _B ³⁺ in order to couple its magnetic moment to the neighbouring ones over the entire temperature interval between 0 K and the respective Néel temperature.     

Structure and occurrences of ≪ green rust ≫ related new minerals of the ≪ fougérite ≫ group,trébeurdenite and mössbauerite,belonging to the ≪ hydrotalcite ≫ supergroup; how Mössbauer spectroscopy helps XRD.

Mössbauer spectroscopy yields decisive information for interpreting x-ray diffraction (XRD) patterns in the case of ‘green rusts” with intercalated CO $_{3}^{2-}$ anions, i.e. the chemical analogs of the three minerals that constitute within the ? hydrotalcite ? supergroup comprising 44 minerals the “fougèrite” group where the structure stays globally unchanged. The only difference comes from the deprotonation of OH^? ions at the apices of the octahedrons occupied by the Fe cations so that Fe ^{I I} ions become Fe ^{I I I} . Low angle x-ray diffraction using synchrotron radiation displays the presence of many polytypes which reflects the stacking of brucite like layers and anion interlayers so that a 2D long range order of anions stays unchanged from fougèrite to mössbauerite.     

Mößbauereffekt in157Gd und155Gd

Using the Mössbauer technique electric hyperfine interactions of the first excited non-rotational states at 64 keV in¹⁵⁷Gd and at 86.5 keV in¹⁵⁵Gd have been determined in GdF₃ and GdCl₃· 6H₂O. For the ratio of quadrupolmoments the ratiosQ ₆₄ ¹⁵⁷ /Q _g ¹⁵⁷ =1.74±0.04,Q _86.5 ¹⁵⁵ /Q _g ¹⁵⁷ =?0.07 ± 0.21 andQ _g ¹⁵⁵ /Q _g ¹⁵⁷ =0.78 ± 0.06 were found. In addition isomer shifts were observed from which a ratio δ〈r²〉 ₆₄ ¹⁵⁷ /δ〈r²〉 _86.5 ¹⁵⁵ =?2.6±0.15 can be inferred.     

Resonant Raman spectroscopy of ethylene-acetylene copolymers doped with iodine

The relative contents of short and long conjugated chains in ethylene-acetylene copolymers (EAC) are determined by varying the lasing wavelength, as was done earlier for pure poly(acetylene). The Raman spectra of the copolymer samples doped with iodine contain the bands attributed to the iodine polyions I ₃ ^? and I ₅ ^? Unlike poly(acetylene), the ethylene-acetylene copolymer is characterized by the Raman spectra in which the intensities of the bands assigned to the I ₅ ^? polyions are higher than those of the I ₃ ^? polyions even at low degrees of doping. The structural features responsible for this difference are discussed.     

129I-Mössbauer study of molecular dynamics in the organic superconductor β-(BEDT-TTF)2I3

¹²⁹ I-Mössbauer spectroscopy was applied to study the organic superconductor β _H -(BEDT-TTF)₂ I ₃ withT _c=8 K. The measurements were performed in the temperature range 1.4 K to 160 K. A detailed analysis of the well-resolved spectra, including transmission integral fits, revelas information about the hyperfine interactions and the local binding strength (f-factor) for the terminal and central sites of the linear and symmetricI ₃ ^? anion. A change in the local Debye temperature of both sites of theI ₃ ^? anions is observed around 120 K, where a phase transition was monitored by other methods. Most interesting with respect to the superconducting properties is a change of the relative intensities of the terminal and central iodine sites, which starts below 10 K and increases down to 1.4 K. This behaviour may be attributed to a libral motion of the iodine molecules and seems to be connected with the occurence of superconductivity in this system.     

Comparison of electron spin polarization of P 870 + Qa a − observed in Zn2+-containing and Fe2+-depleted bacterial reaction centers

Recently, a general model has been developed to explain electron spin polarized (ESP) electron paramagnetic resonance (EPR) signals found in systems where radical pairs are formed sequentially. The photosynthetic bacterial reaction center (RC) is such a system in which we can experimentally vary parameters (lifetime, structure, and magnetic interactions in the sequentially formed radical pairs) that affect ESP development in order to test this model. In Fe²⁺-depleted transfer step from intermediate radical pair, P ₈₇₀ ⁺ Q _a ^? which is produced in an electron transfer step from intermediate radical pair, P ₈₇₀ ⁺ I^?. (P ₈₇₀ ⁺ is the oxidized primary donor, a special pair of bacteriochlorophyll molecules, I^? is the reduced bacteriopheophytin acceptor, and Q _a ^? is the reduced primary quinone acceptor.) The lifetime of P ₈₇₀ ⁺ I^? can be shortened relative to the lifetime of P ₈₇₀ ⁺ I^? in Fe²⁺-depleted RCs by substitution of Zn²⁺. We report the first observation of X-band and Q-band ESP EPR signals due to P ₈₇₀ ⁺ Q^? from bacterial reaction centers that contain Zn²⁺. Comparison of these signals to those observed from Fe²⁺-depleted bacterial reaction centers shows intensity differences and g-factor shifts. The results are discussed in terms of the general sequential radical pair model.     

Mössbaueruntersuchungen an195Pt und201Hg

Using the Mössbauer technique the magnetic hyperfine splitting of the 130 keV transition in¹⁹⁵Pt has been observed in a Pt-Fe alloy. The derived magnetic moment is μ₁₃₀=(0.81 _?0.25 ^+0.13 μ _k . Isomershift measurements with the 130 keV and the 99 keV transitions in alloys yielded Δ〈r ²〉₁₃₀/Δ〈r ²〉₉₉=1.5±0.2 for the ratio of the changes in the mean square charge radius of the two excited states. From isomershifts of the 99 keV transition in compounds an estimate of Δ〈r ²〉₉₉/〈r ²〉=?(1.6 _?0.9 ^+4.4 ) · 10^?4 is made for the change in radius of the first excited state. The linewidth of the Mössbauer spectrum of the 32.2 keV transition in²⁰¹Hg gives a lower limit of 0.1 ns for the half-life of the second excited state. The results are compared with values for other nuclides in this mass region.     

The role of additional anions in microporous aluminosilicates with cancrinite-type framework

Microporous framework aluminosilicates with the cancrinite- and sodalite-type structures containing NO ₃ ^? , CO ₃ ^2? , SO ₄ ^2? and PO ₄ ^3? , as extra-framework anions were synthesized under hydrothermal conditions at temperatures from 160 to 200°C. SO ₄ ^2? exhibits the highest affinity to cancrinite structure at the competition of various X anions. Chemical composition, X-ray diffractometry characteristics, and IR spectra of the compounds obtained, as well as kinetics and mechanism of thermal transformations of nitrate counterpart of cancrinite, were studied.     

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.     

pH Dependence of the Au-CN Species Adsorbed onto Activated Carbon — Comments

In a recent paper by McGrath et al. [Hyp. Interact. 139/140 (2002), 471] the authors appear to have overlooked a body of prior work on the aurocyanide activated carbon system based on X-ray photoelectron spectroscopy. Unlike Mössbauer spectroscopy, limited to chemical state interpretations for a single absorber, XPS is usually capable or both quantitative chemical state assignment and stoichiometry for most atoms within the system. This earlier work shows that rather than producing a mixture of Au(CN) ₂ ^? and AuCN the effect of acid on the aurocyanide adsorbed on activated carbon is to actually produce limited chain length oligomers such as the tetramer Au₄(CN) ₅ ^? . It clearly demonstrates the evolution of bridging (N_b) and terminal (N_t) nitrogen atoms with the relative concentration (for both N?:?Au and N_b?:?N_t) terminating at a stoichiometric ratio indicative of the oligomer. Other shortcomings of the paper in question are discussed.     

Relaxation phenomena in Cr3+ doped Al2O3−Fe 2 57 O3 systems

Mössbauer absorption spectra have been measured for Cr³⁺ doped Al₂O₃?Fe ₂ ⁵⁷ O₃ systems for different values of the Cr³⁺ concentration at room temperature. The cross relaxation between Fe³⁺ and Cr³⁺ ions, which destroys the paramagnetic hyperfine structure of Fe⁵⁷ observed in undoped Al₂O₃?Fe ₂ ⁵⁷ O₃, is thoroughly studied. The experimental results suggest a new kind of cross-relaxation process involving three spins, i.e. two Fe³⁺.ions and one Cr³⁺. The process, though it is a higher-order one, is highly effective because it is energy-conserving.     

A new method for measuring atomic diffusion constant in non-crystalline materials using mössbauer spectroscopy

A new method for measuring atomic diffusion is presented. We prepare artificially modulated structure of Fe₇₀ Si₃₀/Si and we follow the time variation of magnetic iron atom by Mössbauer spectroscopy. It is possible to show that this concentration is related to an apparent difusion constant \(\tilde D_\Lambda \) by $$Ln\frac{{C_m (t)}}{{C_m (o)}} = - \frac{{8\pi ^2 }}{{\Lambda ^2 }} \tilde D_\Lambda t$$ where Λ is the wavelength of the modulation. The interdiffusion constant is found to be 9.5±0.3 . 10^?26 m². s^?1 at 420 K and 1.85±0.1 . 10^?25 m².s^?1 at 450 K.     

g-factor of the 4 1 + rotational state of160Dy

By use of Ge-detectors of the OSIRIS-collaboration [1] in connection with the 12 detector IPAC apparatus of our laboratory [2] a precise measurement of theg-factor of the 4 ₁ ⁺ rotational state of¹⁶⁰Dy was performed. The directional correlations of the threeγ-γ cascades, 1003-197 keV, 1103-197 keV and 1115-197 keV, which are weakly populated in the decay of 72.3 d¹⁶⁰Tb were observed simultaneously. The integral rotations in the static hyperfine field of DyTb at 4.2 K were measured. Theg-factorg(4 ₁ ⁺ )=+0.350(20) was derived. By comparison with the magnetic splitting of the 2 ₁ ⁺ rotational state observed in the same environment by a Mössbauer experiment [3] the ratio of the twog-factors was derived as g(4 ₁ ⁺ )/g(2 ₁ ⁺ )=+ 0.91(5). For the high energy lines we derived from the measured directional correlations the E1/M2 mixing parameters: δ(1003 keV)=+0.005(4); δ(1103 keV)=?0.020(22), and δ(1115 keV)=+0.010(4)