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At least 19 records

Temperature dependence of Fe/++/ crystal field spectra - Implications to mineralogical mapping of planetary surfaces

Results are reported of Fe(++) crystal field spectral measurements for olivines and pyroxenes up to 400 C. The results are correlated with crystal structure data at elevated temperatures, and the validity of remote-sensed identifications of minerals on hot surfaces of the moon and Mercury is assessed. Two techniques were used to obtain spectra of minerals at elevated temperatures using a spectrophotometer. One employed a diamond cell assembly or a specially designed sample holder to measure polarized absorption spectra of heated single crystals. For the other technique, a sample holder was designed to attach to a diffuse reflectance accessory to produce reflectance spectra of heated powdered samples. Polarized absorption spectra of forsterite at 20-400 C are shown in a graph. Other graphs show the temperature dependence of Fe(++) crystal field bands in olivines, the diffuse reflectance spectra of olivine at 40-400 C, the polarization absorption spectra of orthopyroxene at 30-400 C, the diffuse reflectance spectra of pigeonite at 40-400 C, and unpolarized absorption spectra of lunar pyroxene from Apollo 15 rock 15058.

Sung, C.-M.↗

Crystal field and magnetic properties of ErH3

Magnetization and magnetic susceptibility measurements have been made in the temperature range 1.3 to 4.2 K on powdered samples of ErH3. The susceptibility exhibits Curie-Weiss behavior from 4.2 to 2 K, and intercepts the negative temperature axis at 1.05 + or - 0.05 K, indicating that the material is antiferromagnetic. The low field effective moment is 6.77 + or - 0.27 Bohr magnetons per ion. The magnetization exhibits a temperature independent contribution, the slope of which is (5 + or - 1.2) times 10 to the minus 6 Weber m/kg Tesla. The saturation moment is 3.84 + or - 0.15 Bohr magnetons per ion. The results can be qualitatively explained by the effects of crystal fields on the magnetic ions. No definitive assignment of a crystal field ground state can be given, nor can a clear choice between cubically or hexagonally symmetric crystal fields be made. For hexagonal symmetry, the first excited state is estimated to be 86 to 100 K above the ground state. For cubic symmetry, the splitting is of the order of 160 to 180 K.

Flood, D. J.↗

Crystal field and magnetic properties

Magnetization and magnetic susceptibility measurements have been made in the temperature range 1.3 to 4.2 K on powdered samples of ErH3. The susceptibility exhibits Curie-Weiss behavior from 4.2 to 2 K, and intercepts the negative temperature axis at theta = 1.05 + or - 0.05 K, indicating that the material is antiferromagnetic. The low field effective moment is 6.77 + or - 0.27 Bohr magnetons per ion. The magnetization exhibits a temperature independent contribution, the slope of which is (5 + or - 1.2) x 10 to the -6th Weber m/kg Tesla. The saturation moment is 3.84 + or - 1 - 0.15 Bohr magnetons per ion. The results can be qualitatively explained by the effects of crystal fields on the magnetic ions. No definitive assignment of a crystal field ground state can be given, nor can a clear choice between cubically or hexagonally symmetric crystal fields be made. For hexagonal symmetry, the first excited state is estimated to be 86 to 100 K above the ground state. For cubic symmetry, the splitting is on the order of 160 to 180 K.

Flood, D. J.↗

Polarized crystal-field spectra of micro particles of the moon

The instrumentation used in the investigation is considered, giving attention also to a block diagram of the apparatus used for measuring crystal-field spectra. The basic object of the studies was to identify the states of transition elements in lunar crystals in order to obtain information on the chemistry of their crystallization history. After spectral measurements were obtained, the crystals were analyzed for major and minor elements using the electron microprobe. Mineral spectra are considered, giving attention to pyroxene, olivine, plagioclase, and lunar glasses.

Mao, H. K.↗

Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

Freund, F.↗

High temperature crystal field spectra of transition metal-bearing minerals - Relevance to remote-sensed spectra of planetary surfaces

It is pointed out that transition metal ions in silicate minerals, glasses, and crystalline and amorphous oxyhydroxides and salts contribute to the visible-near infrared spectral profiles of planetary surfaces. Investigations are conducted to obtain spectral information which might be helpful in the interpretation of the remote-sensed spectra of planetary surfaces. A description is presented of the results of high temperature crystal field spectral measurements of a variety of heated minerals containing Cr(3+), Fe(3+), Fe(++), and Mn(++) ions in different coordination symmetries, taking into account a correlation of the temperature-induced variations with those previously observed for octahedrally coordinated Fe(++)-bearing silicates. The employed experimental methods are also discussed, giving attention to the preparation of the samples, the determination of the absorption spectra, electron microprobe analyses, and the curve fitting procedure.

Parkin, K. M.↗

Crystal field spectra of lunar pyroxenes.

Absorption spectra in the visible and near infrared regions have been obtained for pyroxene single crystals in rocks from the Apollo 11, 12, 14, and 15 missions. The polarized spectra are compared with those obtained from terrestrial calcic clinopyroxenes, subcalcic augites, pigeonites, and orthopyroxenes. The lunar pyroxenes contain several broad, intense absorption bands in the near infrared, the positions of which are related to bulk composition, Fe(2+) site occupancy and structure type of the pyroxene. The visible spectra contain several sharp, weak peaks mainly due to spin-forbidden transitions in Fe(2+). Additional weak bands in this region in Apollo 11 pyroxenes are attributed to Ti(3+) ions. Spectral features from Fe(3+), Mn(2+), Cr(3+), and Cr(2+) were not observed.

Burns, R. G.↗

Crystalline sulfur dioxide: Crystal field splittings, absolute band intensities and complex refractive indices derived from infrared spectra

The infrared absorption spectra of thin crystalline films of sulfur dioxide at 90 K are reported in the 2700 to 450/cm region. The observed multiplicity of the spectral features in the regions of fundamentals is attributed to factor group splittings of the modes in a biaxial crystal lattice and the naturally present minor S-34, S-36, and O-18 isotopic species. Complex refractive indices determined by an iterative Kramers-Kronig analysis of the extinction data, and absolute band strengths derived from them, are also reported in this region.

Khanna, R. K.↗

Crystal Field Effects and Siderophile Element Partitioning: Implications for Mars HSE Geochemistry

Analyses of martian (SNC) meteorites indicate that Pt abundances do not vary much compared to other highly siderophile elements (HSE). Therefore, Jones et al. [1] inferred that D(Pt) during basalt petrogenesis was of order unity. This inference was at odds with previously published experiments that gave a D(sub ol/liq) for Pt of approx. 0.01 [2]. Because olivine is likely to be an important constituent of any reasonable martian mantle, the implication of these findings is that minor minerals must have D(Pt) much greater than 1, which seemed improbable. However, not only did the SNC evidence point to a D(sub ol/liq) approx. equal to 1, but so did plots of D(sub ol/liq) vs. ionic radius (Onuma diagram). The ionic radius of Pt(2+) suggested that D(sub ol/liq) for Pt was of order unity, in agreement with the inferences from SNC meteorites. New experiments have failed to detect measurable Pt in olivine, even at high oxygen fugacities [3]. Therefore, some other parameter, other than ionic charge and radius, must hold sway during olivine liquid partitioning of Pt.

Jones, John H.↗

Further characterization of spectral features attributable to titanium on the moon

The following transitions are observed in the electronic absorption spectra of lunar titanaugites: Fe(2+) spin-allowed and spin-forbidden crystal field; Ti(3+) spin allowed and Jahn-Teller split crystal field; Ti(3+)-Ti(4+) CT; Fe(2+)-Ti(4+) CT; and O(2-)-Fe(2+), Ti(3+), Ti(4+) CT. Of these, the transitions involving Ti(3+) are unique to lunar or nonferric-bearing titanaugites. All titanaugites have the Fe(2+) crystal field and Fe(2+)-Ti(4+) CT transitions in common. These features in the diffuse reflectance spectra of lunar materials give rise to the '1.0 band' and to the observed absorption around 0.5-0.6 micron, respectively. Since regolith contains a variety of phases with coexisting Fe(2+), Ti(3+), and Ti(4+) ions, several metal-metal charge transfer processes are possible.

Burns, R. G.↗

Computational modelling of Er(3+): Garnet laser materials

The Er(3+) ion has attracted a lot of interest for four reasons: (1) Its (4)I(sub 13/2) yields (4)I(sub 15/2) transition lases in the eyesafe region near 1.5 micron; (2) the (4)I(sub 13/2) transition lases near 2.8 micron, an important wavelength for surgical purposes; (3) it displays surprisingly efficient upconversion with lasing observed at 1.7, 1.2, 0.85, 0.56, 0.55, and 0.47 micron following 1.5 micron pumping; and (4) it has absorption bands at 0.96 and 0.81 micron and thus can be diode pumped. However, properties desirable for upconversion reduce the efficiency of 1.5 and 3 micron laser operation and vice versa. Since all of the processes are influenced by the host via the crystal field induced stark splittings in the Er levels, this project undertook modelling of the host influence on the Er lasinng behavior. While growth and measurement of all ten Er(3+) doped garnets is the surest way of identifying hosts which maximize upconversion (or conversly, 1.5 and 3 micron performance), it is also expensive - costing approximately $10,000/material or approximately $100,000 for the materials computationally investigated here. The calculations were performed using a quantum mechanical point charge model developed by Clyde Morrison at Harry Diamond Laboratories. The programs were used to fit the Er:YAG experimental energy levels so that the crystal field parameters, B(sub nm) could be extracted. From these radial factors, rho (sub n) were determined for Er(3+) in garnets. These, in combination with crystal field components, Anm, available from X-ray data, were used to predict energy levels for Er in the other nine garnet hosts. The levels in Er:YAG were fit with an rms error of 12.2/cm over a 22,000/cm range. Predicted levels for two other garnets for which literature values were available had rms errors of less than 17/cm , showing the calculations to be reliable. Based on resonances between pairs of calculated stark levels, the model predicts GSGG as the best host for 1.5 micron laser operation, GSGG or YSAG as the best host for a 2.8 micron operation, and LuGG as the best host for an upconversion material.

Spangler, Lee H.↗

Energy Levels and Intensity Parameters of Ho3(+) Ions in Y3Al5O12 and Lu3Al5O12

The energy levels of the trivalent lanthanide Ho(sup 3+) in Y3Al5O12 (YAG) and Lu3Al5O12 (LuAG) have been measured. The Stark split levels for the first nine Ho manifolds in these materials have been measured, and the results have been fit to a free ion plus crystal field Hamiltonian to generate a theoretical set of energy levels. Crystal field parameters were varied to determine the best fit between experimental and theoretical energy levels. The energy levels of Ho:LuAG are seen to be very similar to those in Ho:YAG. However, subtle changes resulting from replacing Y(sup 3+) with Lu(sup 3+) in the garnet crystal Y3Al5O12 result in different transition wavelengths in LuAG. This has implications for Ho (sup 5)I7yields (sup 5)I8 lasers operating at approximately 2.1 micrometers. Although the energy levels have been measured previously in Ho:YAG, they have not been measured in Ho:LuAG. A comparison of the energy levels in Ho:YAG measured here show some discrepancies with previous measurements. The consistency of the energy level placement between Ho:LuAG and Ho:YAG indicate that the earlier studies may have some errors in the assignments. Finally, a Judd-Ofelt analysis is performed on Ho:YAG and Ho:LuAG to determine the intensity parameters, and thus, the transition probabilities and branching ratios of the first eight excited manifolds.

Walsh, Brian M.↗

Polymer crystallization in a temperature gradient field with controlled crystal growth rate

A method is described for studying the influence of a temperature gradient on the crystallization of quiescent polymer melts. The apparatus used consists of two brass plates with embedded electrical resistance heaters and cooling coils. The crystallizations experiments were conducted by placing polymer specimens between the paltes, and manually adjusting heaters and cooling fluids for temperature control. Linear polyethylene, isotactic polyprophylene, and a high density polyethylene were used. It is concluded that the role of a temperature gradient in producing oriented crystallization is in producing conditions which lead the spherulitic growth pattern to proceed primarily in one direction. Steep gradients diminish the penetration of supercooling and favors oriented growth.

Hansen, D.↗