排序方式： 共有16条查询结果，搜索用时 15 毫秒
1.
M. Wildner 《Physics and Chemistry of Minerals》1996,23(8):489-496
Polarized electronic absorption spectra of the kieserite-type compounds CoSO4 · H2O and CoSeO4 · H2O have been obtained at room temperature (spectral range 35 000-5000 cm-1) and at liquid nitrogen temperature (visible spectral region), using microscope-spectrometric techniques. The spectra are interpreted and evaluated in terms of a tetragonal crystal field formalism for the d7 configuration, in regard to the pseudotetragonal elongation of the CoO4(H2O)2 octahedra, known from previous X-ray structure investigations, employing the tetragonal parameters Dq, Dt, and Ds, and the Racah parameters B and C. The observed and calculated energy levels are in good agreement for the following parameter sets: CoSO4 · H2O: Dq=826, Dt=40, Ds=350, B=856, C=3580 cm-1; CoSeO4· H2O: Dq=817, Dt=44, Ds=406, B=841, C=3490 cm-1; corresponding ‘cubic’ crystal field strengths Dqcub are 803 and 792 cm-1, respectively. The values of Dq(cub), Racah B and C are in the common range for Co2+ ions in (pseudo) octahedral fields of oxygen ligands, and their differences in CoSO4· H2O compared to CoSeO4 · H2O are consistent with somewhat different mean Co-O bond lengths and with a slightly higher covalent contribution to Co-O bonding in the selenate compound. The values found for the parameter Dt, which is directly correlated to the extent of tetragonal distortion, are much lower than expected from purely geometrical considerations, thus confirming a significantly higher position of H2O ligands in the spectrochemical series compared to oxygen ligands belonging to SO4 or SeO4 groups. 相似文献
2.
Polarized single crystal absorption spectra, in the spectral range 40 000–5 000 cm-1, were obtained on Co2+ in trigonally distorted octahedral oxygen fields of buetschliite-type K2Co(SeO3)2 (I), K2Co2(SeO3)3 (II) and zemannite-type K2Co2(SeO3)3 · 2H2O (III). Site symmetries of Co2+ are
m (D3d) in I, 3m (C3v) in II, and 3 (C3) in III. The spectra can be interpreted on the basis of an electric dipole mechanism, wherein transitions of Co2+ in the centrosymmetric site in I gain intensity from dynamic removal of the inversion centre by vibronic coupling. In accordance with the elongation of the CoO6 octahedra along the trigonal axis, the split component E(g) of the ground state 4T1g in octahedral fields is the ground state in all three compounds. Trigonal field parameters Dq(trig), D, D and the Racah parameters B have been fitted to the energies of spin allowed transitions (293 K) as follows: I: 744, 94, -16, and 838 cm-1, resp.; II: 647, 227, 42, and 798 cm-1, resp.; III: 667, 181, 21, and 809 cm-1, respectively. Racah parameters C were estimated from the energy of some observed spin-forbidden transitions to be 3770 (I), 3280 (II), and 3465 cm-1 (III). Values of Dq and of the Racah parameters B and C indicate slight differences of Co2+-O bonding in I as compared to II and III, with somewhat higher covalency in compounds II and III which contain face-sharing CoO6 octahedra with short Co-Co contacts. Also, in II and III the observed D values do not agree with theoretical D values, predicted from the magnitude of the mean octahedral distortions. 相似文献
3.
Polarized optical absorption spectra of Mn(IV) in octahedral crystal fields of Mn(SeO3)2 have been studied by means of microscope-spectrometry in the range 40000-4000 cm?1 and at temperatures between 113 K and 293 K. Intense charge-transfer absorptions (linear absorption coefficient α ? 30000 cm?1) completely mask the d-d transitions in the UV and VIS region above ≈23000 cm?1. The optical electronegativity χ opt of Mn(IV) in Mn(SeO3)2 is estimated to be 2.7. In accordance with the d 3 configuration of tetravalent manganese three d-d bands observed at ambient temperatures at 13250, 14137 (α≈50 cm?1) and ≈18500 cm?1 (α≈500–800 cm?1) are assigned to the spin forbidden 4 A 2g →2 E g and 4 A 2g →2 T 1g transitions as well as to the first spin allowed 4 A 2g →4 T 2g transition, respectively. These assignments allow the calculation of the following ligand field parameters: Dq ≈ 1850 cm?1, B 55 = 869 cm?1 (β 55 = 0.82), and C = 2346 cm?1 (293 K). 相似文献
4.
Pinto Viter Magalhães Massonne Hans-Joachim Wildner Wilson Hartmann Léo Afraneo Debruyne David Theye Thomas 《Mineralogy and Petrology》2019,113(6):765-782
Mineralogy and Petrology - Mafic-ultramafic intrusions within continental flood basalt terrains are frequently associated with Cu-Ni-PGE mineralization. This study aims to constrain the... 相似文献
5.
Orange, ochre-coloured, light green and dark blue varieties of kyanite, ideally Al2SiO5, from Loliondo, Tanzania, have been characterised by electron microprobe analysis and polarised infrared and optical absorption spectroscopy. All colour varieties show elevated Fe contents of 0.39 to 1.31 wt.% FeO, but Ti contents only in the range of the EMP detection limit. Orange and ochre-coloured crystals have Mn contents of 0.23 and 0.06 wt.% MnO, respectively, the dark blue kyanite contains 0.28 wt.% Cr2O3, while the light green sample is nearly free from transition metal cations other than Fe. Polarised infrared spectra reveal OH defect concentrations of 3 to 17 wt.ppm H2O with structural OH defects partially replacing the OB (O2) oxygen atoms. Polarised optical absorption spectra show that the colour of all four varieties is governed by crystal field d-d transitions of trivalent cations, i.e. Fe3+ (all samples), Mn3+ (orange and ochre) and Cr3+ (blue kyanite), replacing Al in sixfold coordinated triclinic sites of the kyanite structure. Intervalence charge transfer, the prevalent colour-inducing mechanism in ‘usual’ (Cr-poor) blue kyanites, seems to play a very minor, if any, role in the present samples. Crystal field calculations in both a ‘classic’ tetragonal and in the semiempirical Superposition Model approach, accompanied by distance- and angle-least-squares refinements, indicate that Fe3+ preferably occupies the Al4 site, Cr3+ prefers the Al1 and Al2 sites, and Mn3+ predominantly enters the Al1 site. In each case specific local relaxation effects were observed according to the crystal chemical preferences of these transition metal cations. Furthermore, the high values obtained in the calculations for the interelectronic repulsion parameter Racah B correspond to a high ionic contribution to Me3+–O bonding in the kyanite structure. In the particular case of the blue sample, band positions specifically related to the high Racah B value enable this ‘unusual’ type of blue colouration of kyanite solely due to Cr3+ cations. 相似文献
6.
Angela Ullrich Ronald Miletich Tonci Balic-Zunic Lars Olsen Fabrizio Nestola Manfred Wildner Haruo Ohashi 《Physics and Chemistry of Minerals》2010,37(1):25-43
A compressional study of (Na,Ca)(Ti3+,Mg)Si2O6-clinopyroxenes was carried out at high pressures between 10−4 and 10.2 GPa using in situ single-crystal X-ray diffraction, Raman spectroscopy and optical absorption spectroscopy. Compressional
discontinuities accompanied by structural changes, in particular, the appearance of two distinct Ti3+–Ti3+ distances within the octahedral chains at 4.37 GPa, provide evidence for the occurrence of a phase transition in NaTi3+Si2O6. Equation-of-state parameters are K
0 = 115.9(7) GPa with K′ = −0.9(3) and K
0 = 102.7(8) GPa with K′ = 4.08(5) for the low- and high-pressure range, respectively. The transition involves a C2/c–P
[`1] \overline{1} symmetry change, which can be confirmed by the occurrence of new modes in Raman spectra. Since no significant discontinuity
in the evolution of the unit-cell volume with pressure has been observed, the transition appears to be second-order in character.
The influence of the coupled substitution Na+Ti3+↔Ca2+Mg2+ on the static compression behavior and the structural stability has been investigated using a sample of the intermediate
composition (Na0.54Ca0.46)(Mg0.46Ti0.54)Si2O6. No evidence for a deviation from continuous compression behavior has been found, neither in lattice parameter nor in structural
data and the fit of a third-order Birch–Murnaghan equation-of-state to the pressure–volume data yields a bulk modulus of K
0 = 109.1(5) GPa and K′ = 5.02(13). Raman and polarized absorption spectra have been compared to NaTiSi2O6 and reveal major similarities. The main driving force for the phase transition in NaTi3+Si2O6 is the localization of the Ti3+
d-electron and the accompanying distortion, which is suppressed in the (Na,Ca)(Ti3+,Mg)Si2O6-clinopyroxene. 相似文献
7.
Synthetic, flux-grown uvarovite, Ca3Cr2 [SiO4]3, was investigated by optical methods, electron microprobe analysis, UV-VIS-IR microspectrometry, and luminescence spectroscopy. The crystal structure was refined using single-crystal X-ray CCD diffraction data. Synthetic uvarovite is optically isotropic and crystallizes in the “usual” cubic garnet space group Ia3¯d [a=11.9973 Å, Z=8; 21524 reflections, R1=2.31% for 454 unique data and 18 variables; Cr–O=1.9942(6), Si–O=1.6447(6), Ca–Oa=2.3504(6), Ca–Ob= 2.4971(6) Å]. The structure of Ca3Cr2[SiO4]3 complies with crystal-chemical expectations for ugrandite group garnets in general as well as with predictions drawn from “cubically averaged” data of non-cubic uvarovite–grossular solid solutions (Wildner and Andrut 2001). The electronic absorption spectra of Cr3+ in trigonally distorted octahedra of synthetic uvarovite were analyzed in terms of the superposition model (SM) of crystal fields. The resulting SM and interelectronic repulsion parameters are =9532 cm?1, =4650 cm?1, power law exponent t 4=6.7, Racah B35=703 cm?1 at 290 K (reference distance R 0=1.995 Å; fixed power law exponent t 2=3 and spin-orbit parameter ζ=135 cm?1). The interelectronic repulsion parameters Racah B 55=714 cm?1 and C=3165 cm?1 were extracted from spin-forbidden transitions. This set of SM parameters was subsequently applied to previously well-characterized natural uvarovite–grossular solid solutions (Andrut and Wildner 2001a; Wildner and Andrut 2001) using their extrapolated Cr–O bond lengths to calculate the energies of the spin-allowed bands. These results are in very good agreement with the experimentally determined band positions and indicate the applicability of the superposition model to natural 3d N prevailing systems in geosciences. Single-crystal IR absorption spectra of synthetic uvarovite in the region of the OH-stretching vibration exhibit one isotropic absorption band at 3508 cm?1 at ambient conditions, which shifts to 3510 cm?1 at 77 K. This band is caused by structurally incorporated hydroxyl groups via the (O4H4)-hydrogarnet substitution. The water content, calculated using an integral extinction coefficient ?=60417 cm?2 l mol?1, is c H2O=33 ppm. 相似文献
8.
The IR spectrum of an alpine, hydrothermally formed diopside containing 17 wt ppm H2O consists of three main OH absorption bands centred at 3647, 3464 and 3359 cm−1. Jadeite from a Californian vein occurrence is characterised by bands at 3616 and 3557 cm−1 and contains about 197 wt ppm H2O. Based on the pleochroic scheme of the OH absorption bands in diopside, OH defect incorporation models are derived on the
basis of fully occupied cation sites and under the assumption of M1 and M2 site vacancies; OH defects replacing O2 oxygen
atoms are most common. The less pronounced OH pleochroism and the broad band absorption pattern of jadeite indicate a high
degree of OH defect disordering. The pleochroic scheme of the main absorption bands at 3616 and 3557 cm−1 implies partial replacement of O2 oxygen atoms by OH dipoles pointing to vacant Si sites. Under the assumption of M1 and
M2 site vacancies, O1–H and O2–H defects are also derivable. OH incorporation modes assuming Si-vacancies should be considered
for jadeite-rich clinopyroxenes formed in deep crust and upper mantle regions. 相似文献
9.
L. Nasdala M. Wildner R. Wirth N. Groschopf D. C. Pal A. Möller 《Mineralogy and Petrology》2006,86(1-2):1-27
Summary Effects of the impact of natural long-term irradiation with alpha particles in one chamosite and one cordierite sample were
characterised in detail using electron microprobe, Raman microprobe, optical absorption spectroscopy (cordierite only), and
transmission electron microscopy (TEM; cordierite only) analysis. In both cases, the impact of 4He cores (alpha particles) that were emitted from actinide-bearing mineral inclusions has caused the formation of radiation
damage haloes in the host mineral. These haloes have maximum radii of about 33 μm (chamosite) and 47 μm (cordierite). They
show notably changed optical properties, i.e., intensified absorption of light as recognised by brown (chamosite) and yellow
(cordierite) pleochroism and enhanced or even anomalous interference colours. In spite of the significant disturbance of their
short range order, alpha particle haloes are characterised by generally low degrees of structural radiation damage. This is
indicated by rather moderate broadening of vibrational bands and, in the case of cordierite, apparently undisturbed electron
diffraction patterns in the TEM. Intensive damage, virtually close to an amorphous state, was only found in cordierite up
to a few tens of nanometres away from actinide-bearing inclusions. This damage is mainly assigned to recoils of heavy nuclei
upon emission of an alpha particle, which have particle trajectory lengths that are three orders of magnitude shorter than
those of the alpha particles. Similar to observations on biotite, alpha particle haloes in chamosite and cordierite as observed
in the optical microscope may be considered as representative of a very early stage of the metamictisation process. 相似文献
10.
Manfred Wildner Gerald Giester Monika Kersten Klaus Langer 《Physics and Chemistry of Minerals》2014,41(9):669-680
Polarized electronic absorption spectra of colourless chalcocyanite, CuSO4, have been measured using microscope-spectrometric techniques. The spectra are characterized by a structured and clearly polarized band system in the near-infrared spectral range with components centred at 11,720, 10,545, 9,100, and 7,320 cm?1, which have been assigned to crystal field d–d transitions of Cu2+ cations in pseudo-tetragonally elongated CuO6 polyhedra with point symmetry C i ( \(\bar{1}\) ). The polarization behaviour is interpreted based on a D 2(C 2″) pseudo-symmetry. Crystal field calculations were performed for the actual triclinic point symmetry by applying the Superposition Model of crystal fields, as well as in terms of a ‘classic’ pseudo-tetragonal crystal field approach yielding the parameters Dq (eq) = 910, Dt = 395, and Ds = 1,336 cm?1, corresponding to a cubically averaged Dq cub = 679 cm?1. A comparative survey on crystal fields in Cu2+ minerals shows that the low overall crystal field strength in chalcocyanite, combined with a comparatively weak pseudo-tetragonal splitting of energy levels, is responsible for its unique colourless appearance among oxygen-based Cu2+ minerals. The weak crystal field in CuSO4 can be related to the lower position of the SO4 2? anion compared to, e.g. the H2O molecule in the spectrochemical series of ligands. 相似文献