Optical absorption investigation of Cr3+ ion-bearing minerals in the temperature range 77–797 K

The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr³⁺ was studied for various point symmetries of the Cr³⁺-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr³⁺-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm^-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr³⁺-transitions derived from ⁴ A _2g ⁴ T _2g (F) and ⁴ T _1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr³⁺, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr³⁺-centered octahedra, _loc, were derived on the basis of the R _M-0 ^-5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging r_m-o for all the respective octahedral positions.     

Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions

A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R₁, R₂-sharp line luminescence and spectra of excitation of λ₃- and λ₄-components of R₁-line of Cr³⁺-emission had the following results: (1) The Fe²⁺–Ti⁴⁺ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm⁻¹ if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm⁻¹ in crystals with  ≥ . The energy difference is explained by an expansion of the O_f–O_k, and O_b–O_m edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr³⁺ substitutes for Al compared to the chromium-free case. (2) The Cr³⁺ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr^{3+ 4}A_2g→⁴T_2g(F)(I), →⁴T_1g(F)(II), and →⁴T_1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm⁻¹. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm⁻¹, Dq(b)=1600 cm⁻¹, B(a)=790 cm⁻¹, B(b)=620 cm⁻¹ (errors ca. ±10 cm⁻¹), again in agreement with values extracted from the λ³, λ⁴ excitation spectra. The CF-values of set a are close to those typical of Cr³⁺ substituting for Al in octahedra of other silicate minerals without constitutional OH⁻ as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr³⁺ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr³⁺ in the kyanite structural matrix. The CF-data of Cr³⁺ type b, expecially B, resemble those of Cr³⁺ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997     

Statistical modeling of relative variations in the critical frequencies of the ionospheric F region

Relative variations in the critical frequency of the ionospheric F, region are considered as one of the main sources of information about the characteristics of plasma inhomogeneities in the region of the main ionization maximum and as a substantial factor responsible for the statistics of the decameter signal parameters on radio paths with different lengths. The functions defined on finite intervals are also used in statistical modeling in addition to the available methods. Such a consideration made it possible to remove a restriction, peculiar to previous models, in the form of the requirement that the fourth statistical invariant—excess— should be positive. This makes the generalized statistical model more universal, which is of special importance for high4atitude radio paths. The specified mo del more adequately corresponds to the experimental data, which are characterized by finite intervals where the quantities are measured.     

Arctic sea ice long-term dynamics according to the satellite microwave data

The main results of processing the long-term satellite data in different spectral ranges and with different spatial resolutions used to map Arctic sea ice parameters are presented. The advantages of the methods developed in order to estimate these parameters on the basis of microwave sensor measurements are indicated. The specific features of the long-term dynamics of the main sea ice geophysical parameters (the sea ice area and distribution during the summer minimum, ice age structure and thickness, multiyear ice concentration, times of ice melt and freeze onset, etc.) are presented. The effect of changes in sheet ice on the status of large Arctic mammals is estimated.     

Broadening of electron cyclotron maser emission lines in a nonuniform magnetic field

The formation of cyclotron maser emission lines in a non-uniform (regular or random) magnetic field is studied. In the presence of sufficiently small inhomogeneity, the line shape can be described by a broadened Gaussian profile. In the case of stronger inhomogeneity, the initial Gaussian profile splits into two Gaussian components, which could be observationally perceived as “harmonics.” A relation between the distribution of local magnetic trap sizes and the distribution of the spectral widths of solar radio spikes is derived. Possible applications of the results to the interpretation of solar radio spikes and related problems are discussed.     

Optical absorption spectra of iron ions in vivianite

Absorption bands are determined in polarized optical spectra of vivianite Fe₃(PO₄)₂·8H₂O, recorded at room and low temperatures. These bands are caused by spin-allowed d-d transitions in structurally nonequivalent Fe _A ²⁺ (～11000 cm^-1 (γ-polarization) (and) ～12000 cm^-1 (β-polarization)) (and) Fe _B ²⁺ (～8400 cm^-1 (γ, α-polarization) and ～11200 cm^-1 (α-polarization)) ions. A charge transfer band (CTB) Fe _B ²⁺ +Fe _B ³⁺ →Fe _B ²⁺ +Fe _B ²⁺ (～15000 cm^-1) also determined, has polarizing features giving evidence of a change in the Fe _B ²⁺ -Fe _B ³⁺ bond direction, when compared with Fe _B ²⁺ -Fe _B ²⁺ . Bands of exchange-coupled Fe³⁺-Fe³⁺ pairs (～19400, ～20400, ～21300 and ～21700 cm^-1) which appear on oxidation of Fe²⁺ in paired Fe _B octahedra are also characterized.     

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

Increase in Storm Activity in the Kara Sea from 1979 to 2019: Numerical Simulation Data

Doklady Earth Sciences - Wind wave modeling (WAVEWATCH III model) is used to analyze the storm activity in the Kara Sea for the period from 1979 to 2019. The NCEP/CFSR/CFSv2 reanalysis data used as...     

Estimate of relationship between state of subarctic vegetation and climatic parameters

In this study we examined relationships between vegetation phenology and the physical environment across the midlatitudes of the Northern Hemisphere between 1982 and 2007. Spatial correlation, principal component analysis, and canonical correlation analisys—all linear techniques—were applied to monthly time series of the Normalized Difference Vegetation Index (NDVI), derived from an AVHRR sensor, sea ice distribution (SSMR-SSM/I), and air temperature (NCEP/NCAR Reanalysis Atlas). A negative correlation between June NDVI of the tundra belt and sea ice conservation in the coastal zone of Arctic Ocean during summer is possibly forced by broad-scale atmospheric circulation. We developed a model with a single predictor and implemented historical-reconstruction NDVI for a long-term period, including the presatellite era. According to this model, the regional patterns of summer vegetation can be explained by peculiarity of atmospheric circulation in spring.