Mössbauer spectroscopy in the investigation of new mineral–related materials

New materials based on the composition of the mineral schafarzikite, FeSb $_{2}\textit {O}_{4}$ , have been synthesised. $^{57}$ Fe- and $^{121}$ Sb- Mössbauer spectroscopy shows that iron is present as Fe $^{2+}$ and that antimony is present as Sb $^{3+}$ . The presence of Pb $^{2+}$ on the antimony sites in materials of composition FeSb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ induces partial oxidation of Fe $^{2+}_{}$ to Fe $^{3+}$ . The quasi-one-dimensional magnetic structure of schafarzikite is retained in FeSb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ and gives rise to weakly coupled non-magnetic Fe $^{2+}$ ions coexisting with Fe $^{3+}$ ions in a magnetically ordered state. A similar model can be applied to account for the spectra recorded from the compound Co $_{0.5}$ Fe $_{0.5}$ Sb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ .     

Local structure of Fe-doped In 2 O 3 films investigated by X-ray absorption fine structure spectroscopy

$(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ $(x=0.07, 0.09, 0.16, 0.22, 0.31)$ films were deposited on Si (100) substrates by RF-magnetron sputtering technique. The influence of Fe doping on the local structure of films was investigated by X-ray absorption spectroscopy (XAS) at Fe K-edge and L-edge. For the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ films with $x=0.07, 0.09 \mbox{ and } 0.16$ , Fe ions dissolve into $\mathrm{In}_{2}\mathrm{O}_{3}$ and substitute for $\mathrm{In}^{3+}$ sites with a mixed-valence state ( $\mathrm{Fe}^{2+}/\mathrm{Fe}^{3+}$ ) of Fe ions. However, a secondary phase of Fe metal clusters is formed in the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ films with $x=0.22 \mbox{ and } 0.31$ . The qualitative analyses of Fe-K edge extended X-ray absorption fine structure (EXAFS) reveal that the Fe–O bond length shortens and the corresponding Debye–Waller factor ( $\sigma^{2}$ ) increases with the increase of Fe concentration, indicating the relaxation of oxygen environment of Fe ions upon substitution. The anomalously large structural disorder and very short Fe–O distance are also observed in the films with high Fe concentration. Linear combination fittings at Fe L-edge further confirm the coexistence of $\mathrm{Fe}^{2+}$ and $\mathrm{Fe}^{3+}$ with a ratio of ${\sim}3:2$ ( $\mathrm{Fe}^{2+}: \mathrm{Fe}^{3+}$ ) for the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ film with $x=0.16$ . However, a significant fraction ( ${\sim}40~\mbox{at\%}$ ) of the Fe metal clusters is found in the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ film with $x=0.31$ .     

Influence of temperature on the electric,dielectric and AC conductivity properties of nano-crystalline zinc substituted cobalt ferrite synthesized by solution combustion technique

Cobalt–zinc nanoferrites with formulae Co $_{1-x}$ Zn $_{x}$ Fe $_{2}$ O $_{4}$ , where x = 0.0, 0.1, 0.2 and 0.3, have been synthesized by solution combustion technique. The variation of DC resistivity with temperature shows the semiconducting behavior of all nanoferrites. The dielectric properties such as dielectric constant ( $\varepsilon $ ’) and dielectric loss tangent (tan $\delta )$ are investigated as a function of temperature and frequency. Dielectric constant and loss tangent are found to be increasing with an increase in temperature while with an increase in frequency both, $\varepsilon $ ’ and tan $\delta $ , are found to be decreasing. The dielectric properties have been explained on the basis of space charge polarization according to Maxwell–Wagner’s two-layer model and the hopping of charge between Fe $^{2+}$ and Fe $^{3+}$ . Further, a very high value of dielectric constant and a low value of tan $\delta $ are the prime achievements of the present work. The AC electrical conductivity ( $\sigma _\mathrm{AC})$ is studied as a function of temperature as well as frequency and $\sigma _\mathrm{AC}$ is observed to be increasing with the increase in temperature and frequency.     

Spectroscopic properties of Ho 3 + -doped K–Sr–Al phosphate glasses

Trivalent holmium-doped K–Sr–Al phosphate glasses ( $\mathrm{P}_{2}\mathrm{O}_{5}$ – $\mathrm{K}_{2}\mathrm{O}$ –SrO– $\mathrm{Al}_{2}\mathrm{O}_{3}$ – $\mathrm{Ho}_{2}\mathrm{O}_{3}$ ) were prepared, and their spectroscopic properties have been evaluated using absorption, emission, and excitation measurements. The Judd–Ofelt theory has been used to derive spectral intensities of various absorption bands from measured absorption spectrum of 1.0 mol% $\mathrm{Ho}_{2}\mathrm{O}_{3}$ -doped K–Sr–Al phosphate glass. The Judd–Ofelt intensity parameters ( $\varOmega_{\lambda}$ , $\times10^{-20}~\mathrm{cm}^{2}$ ) have been determined of the order of $\varOmega_{2} = 11.39$ , $\varOmega_{4} = 3.59$ , and $\varOmega_{6} = 2.92$ , which in turn used to derive radiative properties such as radiative transition probability, radiative lifetime, branching ratios, etc. for excited states of $\mathrm{Ho}^{3+}$ ions. The radiative lifetimes for the ${}^{5}F_{4}$ , ${}^{5}S_{2}$ , and ${}^{5}F_{5}$ levels of $\mathrm{Ho}^{3+}$ ions are found to be 169, 296, and 317 μs, respectively. The stimulated emission cross-section for 2.05-μm emission was calculated by the McCumber theory and found to be $9.3\times10^{-2 1}~\mathrm{cm}^{2}$ . The wavelength-dependent gain coefficient with population inversion rate has been evaluated. The results obtained in the titled glasses are discussed systematically and compared with other $\mathrm{Ho}^{3+}$ -doped systems to assess the possibility for visible and infrared device applications.     

Structure of some FeII − III hydroxysalt green rusts (carbonate, oxalate, methanoate) from Mössbauer spectroscopy

The abundances of Fe^II and Fe^III environments within green rusts one, GR1s, that intercalate carbonate, oxalate and methanoate (formate) anions are found from Mössbauer spectra for compositions corresponding to [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[CO $_{3}^{2-}$ ?5H₂O]^2???, [Fe $^{\rm II}_{4}$ Fe $^{\rm III}_{2}$ (OH)₁₂]^2?+??[CO $_{3}^{2-}$ ?3H₂O]^2???, [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[C₂O $_{4}^{2-}$ ?4H₂O]^2??? and [Fe $^{\rm II}_{5}$ Fe $^{\rm III}_{2}$ (OH)₁₄]^2?+??[2HCOO^????3H₂O]^2???. These formulae correspond to orders α, β and γ where cation distances are (2 × a ₀), ( $\surd 3$ × a ₀) or a mixture of both leading to (7 × a ₀), where ratio x = {[Fe^III]/[Fe_total]} = 1/4, 1/3 and 2/7, respectively. Anion distributions within interlayers are also devised and long-range orders determined accordingly.     

Background-free detection of trapped ions

We demonstrate a Doppler cooling and detection scheme for ions with low-lying D levels which almost entirely suppresses scattered laser light background, while retaining a high fluorescence signal and efficient cooling. We cool a single ion with a laser on the $^{2}\mathrm{S}_{\mbox{\tiny$1/2$}}\leftrightarrow {^{2}\mathrm{P}}_{\mbox{\tiny$1/2$}}$ transition as usual, but repump via the $^{2}\mathrm{P}_{\mbox{\tiny$3/2$}}$ level. By filtering out light on the cooling transition and detecting only the fluorescence from the $^{2}\mathrm{P}_{\mbox{\tiny$3/2$}}\rightarrow {^{2}\mathrm{S}}_{\mbox{\tiny$1/2$}}$ decays, we suppress the scattered laser light background count rate to 1 s^?1 while maintaining a signal of 29000 s^?1 with moderate saturation of the cooling transition. This scheme will be particularly useful for experiments where ions are trapped in close proximity to surfaces, such as the trap electrodes in microfabricated ion traps, which leads to high background scatter from the cooling beam.     

Effect of Y3+ substitution on the structural,dielectric, and electrical properties of nanosized ZnAl 2 O 4 spinel

In the present work, we have studied the structural, dielectric, and electrical properties of a series of nanosized $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ ( $x = 0.00$ , 0.01, 0.02, 0.03, 0.04, 0.05, 0.07, and 0.10) system prepared by chemical coprecipitation method. Powder X-ray diffraction (XRD) was carried out to study the influence of $\mathrm{Y}^{3+}$ substitution on the crystal structure of these samples. High Resolution Transmission Electron Microscopy (HRTEM) images reveal the nanocrystalline nature of the samples. The Fourier Transform Infrared (FTIR) spectra confirmed the preference of $\mathrm{Y}^{3+}$ ions at the octahedral B site. The variation of dielectric constant and loss tangent (1 kHz to 1 MHz) at room temperature for all the samples show the normal behavior of spinel compounds. AC conductivity study reveals that the conduction is due to small polaron hopping. The electrical modulus analysis shows that nanocrystalline $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ system exhibits non-Debye-type relaxation. The DC electrical resistivity measured in the temperature range 303–373 K was found to increase with temperature and yttrium content.     

Gas-Like Cluster States in Finite Nuclei

Gas-like α cluster states are investigated in ¹⁶O with the use of 4α OCM (orthogonality condition model) and GEM (Gauss expansion method). α-particle condensed state is found slightly above the 4α threshold as the ${0_6^+}$ state. The candidates of the ${\alpha + {^{12}{\rm C}(0_2^+)}}$ rotational states are also found at a few megaelectron volt above the condensate. The ${0_6^+}$ state is shown to have an analogue structure to the Hoyle state ${({^{12}{\rm C}}(0_2^+))}$ and its relation with the α+ Hoyle-like rotational states is also discussed.     

All-carbon detector with buried graphite pillars in CVD diamond

A diamond detector of 3D architecture without any metallization is developed for spectroscopy of ionizing radiation and single particles detection. The carbon electrode system was fabricated using a femtosecond infrared laser ( $\lambda $ = 1,030 nm) to induce graphitization on the surface and inside 4.0  $\times $  4.0  $\times $  0.4 mm $^{3}$ single-crystal chemical vapor deposition diamond slab, resulting in an array of 84 buried graphite pillars of 30  $\upmu $ m diameter formed orthogonally to the surface and connected by surface graphite strips. Sensitivity to ionizing radiation with $^{90}$ Sr $\upbeta $ -source has been measured for the 3D detector and high charge collection efficiency is demonstrated.     

Analysis of the {3\over 2}^{+} heavy and doubly heavy baryon states with QCD sum rules

In this article, we study the ${3\over 2}^{+}$ heavy and doubly heavy baryon states $\varXi^{*}_{cc}$ , $\varOmega^{*}_{cc}$ , $\varXi^{*}_{bb}$ , $\varOmega^{*}_{bb}$ , $\varSigma_{c}^{*}$ , $\varXi_{c}^{*}$ , $\varOmega_{c}^{*}$ , $\varSigma_{b}^{*}$ , $\varXi_{b}^{*}$ and $\varOmega_{b}^{*}$ by subtracting the contributions from the corresponding ${3\over 2}^{-}$ heavy and doubly heavy baryon states with the QCD sum rules, and we make reasonable predictions for their masses.     

Separation efficiency of the MASHA facility for short-lived mercury isotopes

The mass-separator MASHA built to identify Super Heavy Elements by their mass-to-charge ratios is described. The results of the off- and on-line measurements of its separation efficiency are presented. In the former case four calibrated leaks of noble gases were used. In the latter the efficiency was measured via 284 MeV $^{40}$ Ar beam and with using the hot catcher. The ECR ion source was used in both cases. The $\alpha $ -radioactive isotopes of mercury produced in the complete fusion reaction $^{40}$ Ar+ $^{144}$ Sm $\rightarrow ^{184-xn}$ Hg+xn were detected at the mass-separator focal plane. The half-lives and the separation efficiency for the short-lived mercury isotopes were measured. Potentialities of the MEDIPIX detector system have been demonstrated for future use at the mass-separator MASHA.     

A DFG-based cavity ring-down spectrometer for trace gas sensing in the mid-infrared

Continuing studies into an all-diode laser-based 3.3 μm difference frequency generation cavity ring-down spectroscopy system are presented. Light from a 1,560 nm diode laser, amplified by an erbium-doped fibre amplifier, was mixed with 1,064 nm diode laser radiation in a bulk periodically poled lithium niobate crystal to generate 16 μW of mid-IR light at 3,346 nm with a conversion efficiency of $0.05\,\%\,{\text{W}}^{-1}\,{\text{cm}}^{-1}$ . This radiation was coupled into a 77 cm long linear cavity with average mirror reflectivities of 0.9996, and a measured baseline ring-down time of $6.07\pm 0.03\,\upmu{\rm s}$ . The potential of such a spectrometer was illustrated by investigating the $P(3)$ transition in the fundamental $\nu_{3}(F_{2})$ band of ${\text{CH}}_4$ both in a 7.5 ppmv calibrated mixture of ${\text{CH}}_4$ in air and in breath samples from methane and non-methane producers under conditions where the minimum detectable absorption coefficient ( $\alpha_{\rm min}$ ) was $2.8 \times 10^{-8}\,{\rm cm}^{-1}$ over 6 s using a ring-down time acquisition rate of 20 Hz. Allan variance measurements indicated an optimum $\alpha_{\rm min}$ of $2.9\times 10^{-9}\,{\rm cm}^{-1}$ over 44 s.     

A realistic pattern of lepton mixing and masses from $$S_4$$ and CP

We calculate the combined angular-distribution functions of the polarized photons ( $\gamma _1$ and $\gamma _2$ ) and electron ( $e^-$ ) produced in the cascade process $\bar{p}p\rightarrow {^3{D_3}}\rightarrow {^3{P_2}}+\gamma _1 \rightarrow (\psi +\gamma _2)+\gamma _1\rightarrow (e^++e^-)+\gamma _1+\gamma _2$ , when the colliding $\bar{p}$ and $p$ are unpolarized. Our results are independent of any dynamical models and are expressed in terms of the spherical harmonics whose coefficients are functions of the angular-momentum helicity amplitudes of the individual processes. Once the joint angular distribution of ( $\gamma _1$ , $\gamma _2$ ) and that of ( $\gamma _2$ , $e^-$ ) with the polarization of either one of the two particles are measured, our results will enable one to determine the relative magnitudes as well as the relative phases of all the angular-momentum helicity amplitudes in the radiative decay processes ${^3{D_3}}\rightarrow {^3{P_2}}+\gamma _1$ and ${^3{P_2}}\rightarrow \psi +\gamma _2$ .     

Femtosecond relaxation kinetics of highly excited \mathrm{M}_{\mathrm{Na}}^{**} states in CaF2 at 3.2 eV and 4.7 eV

Femtosecond (fs) laser pulses at variable delay times allowed us to track the fast non-radiative transitions between the manifold of highly excited $\mathrm{M}_{\mathrm{Na}}^{**}$ states to the lower lying fluorescent $\mathrm{M}_{\mathrm{Na}}^{*}$ state in CaF₂. Two distinct $\mathrm{M}_{\mathrm{Na}}^{**}$ states of the manifold at 3.16?eV ( $\mathrm{M}_{\mathrm{Na}2}^{**}$ ) and 4.73?eV ( $\mathrm{M}_{\mathrm{Na}3}^{**}$ ) were populated using the second (SH) and third harmonics (TH) of fs laser light at 785?nm. The population kinetics of the fluorescent $\mathrm{M}_{\mathrm{Na}}^{*}$ state in the 2?eV excitation energy range was revealed by depleting its fluorescence centered at 740?nm using fundamental near infrared (NIR) fs laser pulses. The related time constants for $\mathrm{M}_{\mathrm{Na}2,3}^{**}{\sim}{>} \mathrm{M}_{\mathrm{Na}}^{*}$ relaxation amounted to 1.0±0.14?ps and 3.0±0.3?ps upon SH and TH excitation, respectively.     

Growth of strongly textured FeCO 3 thin films for application in research of nuclear quantum optics with ultrashort-pulsed laser deposition

Growth of strongly textured $\mathrm{FeCO}_{3}$ thin films on substrates was achieved with ultrashort-pulsed laser deposition using 810-nm, 46-fs ablation pulses. The crystallinity and composition were verified with X-ray diffraction and Raman spectroscopy. Using Mössbauer spectroscopy, it is shown that the deposited $\mathrm{FeCO}_{3}$ thin films possess the film quality required for application in research of nuclear quantum optics. It is found that a relatively low substrate temperature is crucial for growing a strongly textured film of $\mathrm{FeCO}_{3}$ while avoiding decomposition of $\mathrm{FeCO}_{3}$ into $\mathrm{Fe}_{2}\mathrm{O}_{3}$ and $\mathrm{CO}_{2}$ . This supports the importance of the use of ultrashort-pulsed laser deposition in providing adatoms with high mobility for attaining good crystallinity. The surface morphology was characterized by surface profilometry, scanning electron microscopy and atomic force microscopy. It is found to be significantly affected by changing the ablation laser parameters, including laser fluence, pulse duration, and on-target spot size. The results show that the peak deposition flux must be below approximately 0.03 nm/pulse in order to grow a flat film.     

Backscattering Mössbauer MIMOS II and XRF studies on tektites from different strewn fields

Room temperature ⁵⁷Fe Mössbauer spectroscopy has been used to obtain information on the redox and coordination of iron in tektites. A MIMOS II spectrometer in backscattering geometry has been used in the study, so that no sample preparation at all was required. X-ray fluorescence has been used to determine the composition of the tektites. Mössbauer spectra have been deconvoluted using three extended Voigt-based profiles to allow quantitative analysis of iron atoms valence and coordination. In all tektites, the Fe $^{2+ }$ sites have been distinguished in Fe with octahedral and tetrahedral coordination. The Fe $^{2+}$ octahedral sites show a region of isomer shift (IS) and quadrupole splitting (QS), IS $=$ 1.02–1.14 mm/s and QS $=$ 1.82–2.12 mm/s, relative to $\alpha $ -Fe. The Fe $^{2+ }$ tetrahedral sites show a region of hyperfine parameters of IS = 0.59–0.89 mm/s and QS = 1.14–1.60 mm/s. The Fe³⁺sites show IS = 0.11–0.33 mm/s and QS = 0.02–0.04 mm/s. The Fe³⁺/Fe²⁺ ratio was found to be 0.025–0.149.     

Fomenko–Mischenko Theory, Hessenberg Varieties, and Polarizations

The symmetric algebra ${S(\mathfrak{g})}$ over a Lie algebra ${\mathfrak{g}}$ has the structure of a Poisson algebra. Assume ${\mathfrak{g}}$ is complex semisimple. Then results of Fomenko–Mischenko (translation of invariants) and Tarasov construct a polynomial subalgebra ${{\mathcal {H}} = {\mathbb C}[q_1,\ldots,q_b]}$ of ${S(\mathfrak{g})}$ which is maximally Poisson commutative. Here b is the dimension of a Borel subalgebra of ${\mathfrak{g}}$ . Let G be the adjoint group of ${\mathfrak{g}}$ and let ? = rank ${\mathfrak{g}}$ . Using the Killing form, identify ${\mathfrak{g}}$ with its dual so that any G-orbit O in ${\mathfrak{g}}$ has the structure (KKS) of a symplectic manifold and ${S(\mathfrak{g})}$ can be identified with the affine algebra of ${\mathfrak{g}}$ . An element ${x\in \mathfrak{g}}$ will be called strongly regular if ${\{({\rm d}q_i)_x\},\,i=1,\ldots,b}$ , are linearly independent. Then the set ${\mathfrak{g}^{\rm{sreg}}}$ of all strongly regular elements is Zariski open and dense in ${\mathfrak{g}}$ and also ${\mathfrak{g}^{\rm{sreg}}\subset \mathfrak{g}^{\rm{ reg}}}$ where ${\mathfrak{g}^{\rm{reg}}}$ is the set of all regular elements in ${\mathfrak{g}}$ . A Hessenberg variety is the b-dimensional affine plane in ${\mathfrak{g}}$ , obtained by translating a Borel subalgebra by a suitable principal nilpotent element. Such a variety was introduced in Kostant (Am J Math 85:327–404, 1963). Defining Hess to be a particular Hessenberg variety, Tarasov has shown that ${{\rm{Hess}}\subset \mathfrak{g}^{\rm{sreg}}}$ . Let R be the set of all regular G-orbits in ${\mathfrak{g}}$ . Thus if ${O\in R}$ , then O is a symplectic manifold of dimension 2n where n = b ? ?. For any ${O\in R}$ let ${O^{\rm{sreg}} = \mathfrak{g}^{\rm{sreg}} \cap O}$ . One shows that O ^sreg is Zariski open and dense in O so that O ^sreg is again a symplectic manifold of dimension 2n. For any ${O\in R}$ let ${{\rm{Hess}}(O) = {\rm{Hess}}\cap O}$ . One proves that Hess(O) is a Lagrangian submanifold of O ^sreg and that $${\rm{Hess}} = \sqcup_{O\in R}{\rm{Hess}}(O).$$ The main result of this paper is to show that there exists simultaneously over all ${O\in R}$ , an explicit polarization (i.e., a “fibration” by Lagrangian submanifolds) of O ^sreg which makes O ^sreg simulate, in some sense, the cotangent bundle of Hess(O).     

Laser nanoablation of graphite

Experimental data on laser ablation of highly oriented pyrolitic graphite by nanosecond pulsed UV ( $\lambda =193$  nm) and green ( $\lambda =532$  nm) lasers are presented. It was found that below graphite vaporization threshold $\approx $ 1 J/cm $^{2}$ , the nanoablation regime can be realized with material removal rates as low as 10 $^{-3}$  nm/pulse. The difference between physical (vaporization) and physical–chemical (heating + oxidation) ablation regimes is discussed. Special attention is paid to the influence of laser fluence and pulse number on ablation kinetics. Possibility of laser-induced graphite surface nanostructuring has been demonstrated. Combination of tightly focused laser beam and sharp tip of scanning probe microscope was applied to improve material nanoablation.     

Structural evolution of nanopores and cracks as fundamental constituents of ultrashort pulse-induced nanogratings

We present an extensive study of the underlying structure of femtosecond laser-induced nanogratings in fused silica. To explore the evolution of the three-dimensional structure of the nanopores and cracks, of which the nanogratings consist, we performed small angle X-ray scattering measurements as well as focused ion beam milling and scanning electron microscopy. Our results show that cracks with dimensions of (280  $\times $  25  $\times $  380) nm $^{3}$ and nanopores with typical diameters of (30  $\times $  25  $\times $  75) nm $^{3}$ are formed independent of various illumination parameters. With increasing number of laser pulses the smaller pores fuse to larger structures. Furthermore, the data suggest a cross-sectional change of the pores from cuboidal to ellipsoidal.