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All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Interatomic Auger transitions in maximal valent V and Cr compounds

The sensitivity of the intensities of the L(3)M(23)M(45) and L(3)M(45)M(45) Auger transitions toward the 3d character in the valence band has been demonstrated by using argon ion bombardment as a means of in situ reduction for the valence state of V and Cr in their maximal valent compounds. The selected V(5+) and Cr(6+) compounds were V2O5, NH4VO3, K2Cr2O7, K2CrO4, and CrO3. Auger and X-ray photoelectron spectra of fresh samples were obtained, and the samples were then subjected to ion bombardment of various durations. The subsequent spectra were recorded to monitor possible alterations due to the reduction of the cation valence state. The interatomic to intraatomic transitions of the Auger spectra transitions of the Auger spectra were observed dynamically and in situ. In particular, the intensity of the cation L(3)M(23)N(45) transitions was observed to increase dramatically with ion bombardment. The correlation between the interatomic Auger transition and covalency as well as the movements of the 3d electrons are discussed.

Yin, L. I.↗
NASA NTRS2018

Almahata Sitta MS-MU-011 and MS-MU-012: Formation Conditions of Two Unusual Rocks From the Ureilite Parent Body

Almahata Sitta meteorites are unique polymict breccia, comprising of many different meteorite groups as individual fragments dominated by ureilite lithologies and are considered to be recovered fragments of the asteroid 2008TC3. Recently, two unusual Almahata Sitta samples (MS-MU-011 and MS-MU-012) have been reported that show close petrogenetic relationships to ureilites. MS-MU-011 is a trachyandesite mainly composed of feldspar (plagioclase and anorthoclase) and pyroxene (pigeonite and augite) having ureilitic oxygen isotopic ratios. MS-MU-012 is the first ureilite example (unbrecciated) containing primary plagioclase crystals. The findings of these two rock types are important to better understand formation conditions of ureilites and the evolution of their parent body(s). In this abstract we discuss formation conditions of these ureilite-related rocks using redox state estimate by Fe valence states of plagioclase and olivine cooling rate calculations.

Mikouchi, T.↗
NASA NTRS1971

Photoionization and absorption spectrum of formaldehyde in the vacuum ultraviolet.

The measurements have been conducted in the spectral range from 600 to 2000 A. Integrated oscillator strengths were determined for a number of strong Rydberg transitions above 1200 A. From the photoionization curve the first adiabatic ionization potential was found to be 10.87 plus or minus 0.01 eV. As an aid in interpreting the absorption spectrum, theoretical calculations were made using a single-configuration self-consistent field procedure for the Rydberg states and a model which included mixing between the Rydberg and valence states.

Mentall, J. E.↗
NASA NTRS1998

Modeling and Simulation of Semiconductor Quantum Well Structures and Lasers

In this talk I will cover two aspects of modeling and simulation efforts at NASA Ames Research Center. In the quantum well structure simulation, we typically start from the quantum mechanical calculation of the quantum well structures for the confined/and unconfined eigen states and functions. A bandstructure calculation of the k*p type is then performed for the confined valence states. This information is then used to computer the optical gain and refractive index of the quantum well structures by solving the linearized multiband semiconductor Bloch equations with the many-body interactions included. In our laser simulation, we typically solve the envelope equations for the laser field in space-time domain, coupled with a reduced set of material equations using the microscopic calculation of the first step. Finally I will show some examples of both aspects of simulation and modeling.

Ning, Cun-Zheng↗
NASA NTRS2004

The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity

The intrinsic oxygen fugacity (fO2) imposed on a magma has the ability to influence the crystallization sequence of the melt, as well as the composition of the resulting minerals. fO2 is an easily controlled parameter in the lab, either through gas-mixing equilibria or with a solid-state buffer assemblage. In nature, the fO2 of a closed system is imposed on the system internally through multivalent equilibria involving the phenocryst-melt assemblage. This results in a characteristic oxidation state. The physical parameter used to quantify oxidation state is oxygen fugacity. Iron is the only major rock forming element in basaltic melts to exist in multiple valence states and, therefore, it is commonly used to assess fO2. Traditional methods to quantify fO2 utilize the ferric content of glasses or coexisting Fe-Ti oxides. However, many rocks, such as the Martian meteorites, do not contain the necessary phases or have oxides which have suffered reequilibration, thereby rendering them unmeasureable by current techniques. For these rocks, new methods, utilizing other phases are needed. Mafic minerals have Fe(3+)/SigmaFe ratios that are a function of two factors: 1) crystal chemistry and 2) their intrinsic fO2 during crystallization. Olivine and orthopyroxene, for example, have steric constraints on the extent to which Fe(3+) can be incorporated in their structures, and may not record changes in magmatic fO2 in a way that can easily be measured. The chemistry of clinopyroxene, however, allows for extensive incorporation of Fe(3+) in its crystal structure, making it a potentially useful oxybarometer. To date, there have been few, if any, systematic experimental studies of the variation of the Fe(3+)/SigmaFe ratio as a function of fO2 in clinopyroxene. This study seeks to address this lack of data.

McCanta, M. C.↗
NASA NTRS2017

Oxygen Depletion on the Surface of Mercury: Evidence of Silicon Smelting?

The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft collected data that provided important insights into the structure, chemical makeup, and compositional diversity of Mercury. The X-Ray Spectrometer (XRS) and Gamma-Ray Spectrometer (GRS) onboard MESSENGER provided the first detailed chemical analyses of Mercury's surface. Among the many discoveries included several surprising characteristics about the surface of Mercury, including elevated S abundances (up to 4 percent by weight), low Fe abundances (less than 4 percent by weight), and relatively low O abundances (O/Si ratio of 1.40 plus or minus 0.03). The surface chemistry as determined by MESSENGER has been used to identify up to nine distinct geochemical terranes on Mercury. Numerous modeling and experimental efforts have been undertaken to infer the mineralogy and petrology of mercurian lavas and surface materials. However, all of these efforts have presumed valence states for each of the elements according to the following: Si4+, Ti4+, Al3+, Cr2+, Fe2+, Mn2+, Mg2+, Ca2+, Na+, K+, S2-, Cl-. Based on these valence assignments, cations are charged balanced with the anions O2-, S2-, and Cl- and the compositions are recast in terms of oxides, sulfides, and chlorides. Based on these assumptions, the geochemical terranes that have been identified on Mercury yield O/Si wt. ratios ranging from 1.61 to 1.84, which is substantially higher than the preliminary O/Si ratio of 1.40 plus or minus 0.03 determined by the MESSENGER GRS]. We have re-evaluated the O/Si ratio using the entire MESSENGER dataset to reassess its implications for the geochemistry of Mercury.

McCubbin, F. M.↗
NASA NTRS2016

The Cr Redox Record of fO2 Variation in Angrites. Evidence for Redox Conditions of Angrite Petrogenesis and Parent Body

Angrites represent some of the earliest stages of planetesimal differentiation. Not surprisingly, there is no simple petrogenetic model for their origin. Petrogenesis has been linked to both magmatic and impact processes. Studies demonstrated that melting of chondritic material (e.g. CM, CV) at redox conditions where pure iron metal is unstable (e.g., IW+1 to IW+2) produced angrite-like melts. Alternatively, angrites were produced at more reducing conditions (<IW) with their exotic melt compositions resulting from carbonates in the source or from nebular condensation. Clearly, understanding what role fO2 plays in producing angrite magmas is critical for deciphering their petrogenesis and extending our understanding of primordial melting of asteroids. Calculations for the fO2 conditions of angrite crystallization are limited, and only preliminary attempts been made to understand the changes in fO2 that occurred during petrogenesis. Many of the angrites have phase assemblages which provide conflicting signals about redox conditions during crystallization (e.g., Fe metal and a Fe-Ti oxide with potential Fe3+. There have been several estimates of fO2 for angrites. Most notably, experiments examined the variation of DEu/DGd with fO2, between plagioclase and fassaitic pyroxene in equilibrium with an angrite melt composition. They used their observations to estimate the fO2 of crystallization to be approximately IW+0.6 for angrite LEW 86010. This estimate is only a "snapshot" of fO2 conditions during co-crystallization of plagioclase and pyroxene. Preliminary XANES analyses of V redox state in pyroxenes from D'Orbigny reported changes in fO2 from IW-0.7 during early pyroxene crystallization to IW+0.5 during latter episodes of pyroxene crystallization [15]. As this was a preliminary report, it presented limited information concerning the effects of pyroxene orientation and composition on the V valence measurements, and the effect of melt composition on valence and partitioning behavior of V. A closer examination of fO2 as recorded by Cr valence state in olivine will allow us to test models for primordial melting of chondritic material to produce the angrite parent melts. Here, we report the our initial stages of examining the origin and conditions of primordial melting on the angrite parent body and test some of the above models by integrating an experimental study of Cr and V valence partitioning between olivine [OL] and an angrite melt, with micro-scale determinations of Cr and V oxidation state in OL in selected "volcanic" angrites.

Shearer, Charles K.↗
NASA NTRS1989

Medium-resolution studies of extreme ultraviolet emission from N2 by electron impact - Vibrational perturbations and cross sections of the c4-prime 1Sigma(+)u and b-prime 1Sigma(+)u states

In a crossed-beam experiment the electron-impact-induced fluorescence spectrum of N2 in the extreme ultraviolet is studied at a spectral resolution of up to 0.03 nm. The optically thin experiment obtained the highest-resolution electron-impact emission spectrum of the Rydberg and valence states of N2. The spectral measurements provide the emission cross sections of each of the vibrational transitions of the Carroll-Yoshino and the Birge-Hopfield-II band systems. Laboratory vibrational-excitation cross sections arising from the mutual perturbation of the c4-prime 1Sigma(+)u and b-prime 1Sigma(+)u states by homogeneous configuration interactions are measured from 10 to 400 eV, and a modified Born approximation analytic model is given for them. The analysis leads to accurate band-system oscillator strengths. The relative emission and excitation cross sections each of the vibrational levels are compared. In addition, low-resolution measurements of the cross section of the atomic dissociation fragments (NI, NII, NIII) from 40 to 102 nm are made, and medium-resolution measurements are made of the emission cross section of the c4 1Pi(u), c5-prime 1Sigma(+)u, c5 1Pi(u), and c6-prime 1Sigma(+)u to X 1Sigma(+)g (0,0) transitions.

Ajello, Joseph M.↗
NASA NTRS1990

Matrix elements in the coupled-cluster approach - With application to low-lying states in Li

A procedure is suggested for evaluating matrix elements of an operator between wavefunctions in the coupled-cluster form. The use of the exponential ansatz leads to compact exponential expressions also for matrix elements. Algorithms are developed for summing all effects of one-particle clusters and certain chains of two-particle clusters (containing the well-known random-phase approximation as a subset). The treatment of one-particle perturbations in single valence states is investigated in detail. As examples the oscillator strength for the 2s-2p transition in Li as well as the hyperfine structure for the two states are studied and compared to earlier work.

Martensson-Pendrill, Ann-Marie↗
NASA NTRS2017

Diffusion of Redox-Sensitive Elements in Basalt at Different Oxygen Fugacities

The terrestrial planets and moons of our solar system have differentiated over a range of oxygen fugacity conditions. Basalts formed from magmas on the Earth cover a range of more oxidized states (from approximately IW (iron wustite) plus 2 to approximately FMQ (fayalite-magnetite-quartz) plus 3) than crustal rocks from Mars (IW to approximately IW plus 3), and basalts from the Moon are more reduced than both, ranging from IW to IW minus 2. The small body Vesta differentiated around IW minus 4. Characterization of redox sensitive elements' diffusivities will offer insight into behavior of these elements as a function of f (fugacity of) O2 for these planetary bodies. Here, we report a systematic study of the diffusion of redox-sensitive elements in basaltic melts with varying oxygen fugacities (fO2) for trace elements, V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Since fO2 is an intensive variable that is different for the reservoirs of various planets and moons in our solar system, it is important to characterize how changes in redox states will affect diffusion. We conducted experiments in a piston cylinder device at 1300 degrees Centigrade and 1 gigapascal, at the University of Rochester and NASA Johnson Space Center. We buffered some experiments at Ru-RuO2 (FMQ plus 6.00), and conducted other experiments within either a graphite or Mo capsule, which corresponds to fO2s of either FMQ minus1.2, or FMQ minus 3.00, respectively. Characterizing the diffusivities of redox sensitive elements at different fO2s is important because some elements, like Eu, have varying valence states, such as Eu (sup 2 plus) and Eu (sup 3 plus). Differences in charge and ion radii may lead to differences in diffusivities within silicate melts. This could, lead to formation of a Eu anomaly by diffusion, the magnitude of which may be controlled by the fO2. Characterization of trace element diffusion is also important in understanding trace element fractionation. We found, during the course of our investigation, that not only did the diffusivities of the redox sensitive elements change with fO2, but that the diffusivities of all other analyzed elements also changed. This indicates that not only do changes in valence influence trace elements diffusivities but that the structure of melt may have changed with varying oxygen fugacity, probably due to changes in the speciation of the major element Fe.

Szumila, I.↗
NASA NTRSDate not supplied

Vanadium Valence in MgAl2O4 Spinels at Reducing Conditions (IW to IW-5)

Vanadium is commonly a major or minor element in spinel structured oxides from a wide range of planetary materials [1-3]. Vanadium is stable in multiple valence states of 5+, 4+, 3+, and 2+ in natural systems, and spinel-structured oxides are known to host vanadium in 4+, 3+, and 2+ [4-6]. However, the understanding of 2+ stability at lower fO2 conditions has been hindered by lack of experiments at or below IW-1 conditions [5]. Insufficient experimental data is available due to the difficulty in controlling fO2 at low conditions in general, and the lack of appropriate standards for comparison to natural materials. Our progress on controlling fO2 in high pressure experimental samples has allowed us to create reducing conditions that are appropriate to studying V valence in spinels at fO2 relevant to natural reducing systems [7]. Here we extend this approach to study V in reduced conditions, at high temperatures. After at-tempting shorter durations and lower temperatures, we demonstrated the need for equilibration times > 6 hours at 1600 °C in order to approach equilibrium. Only then can we produce highly equilibrated samples that provide new insights into V valence at low fO2.

oxygen fugacity↗
NASA NTRS2016

The Mineralogy, Geochemistry, and Redox State of Multivalent Cations During the Crystallization of Primitive Shergottitic Liquids at Various (f)O2. Insights into the (f)O2 Fugacity of the Martian Mantle and Crustal Influences on Redox Conditions of Martian Magmas.

The (f)O2 [oxygen fugacity] of crystallization for martian basalts has been estimated in various studies to range from IW-1 to QFM+4 [1-3]. A striking geochemical feature of the shergottites is the large range in initial Sr isotopic ratios and initial epsilon(sup Nd) values. Studies by observed that within the shergottite group the (f)O2 [oxygen fugacity] of crystallization is highly correlated with these chemical and isotopic characteristics with depleted shergottites generally crystallizing at reduced conditions and enriched shergottites crystallizing under more oxidizing conditions. More recent work has shown that (f)O2 [oxygen fugacity] changed during the crystallization of these magmas from one order of magnitude in Y980459 (Y98) to several orders of magnitude in Larkman Nunatak 06319. These real or apparent variations within single shergottitic magmas have been attributed to mixing of a xenocrystic olivine component, volatile loss-water disassociation, auto-oxidation during crystallization of mafic phases, and assimilation of an oxidizing crustal component (e.g. sulfate). In contrast to the shergottites, augite basalts such as NWA 8159 are highly depleted yet appear to be highly oxidized (e.g. QFM+4). As a first step in attempting to unravel petrologic complexities that influence (f)O2 [oxygen fugacity] in martian magmas, this study explores the effect of (f)O2 [oxygen fugacity] on the liquid line of descent (LLD) for a primitive shergottite liquid composition (Y98). The results of this study will provide a fundamental basis for reconstructing the record of (f)O2 [oxygen fugacity] in shergottites and other martian basalts, its effect on both mineral chemistries and valence state partitioning, and a means for examining the role of crystallization (and other more complex processes) on the petrologic linkages between olivine-phyric and pyroxene-plagioclase shergottites.

Shearer, C. K.↗
NASA NTRS1971

Solar wind radiation damage effects in lunar material

The research on solar wind radiation damage and other effects in lunar samples which was conducted to understand the optical properties of lunar materials is reported. Papers presented include: solar radiation effects in lunar samples, albedo of the moon, radiation effects in lunar crystalline rocks, valence states of 3rd transition elements in Apollo 11 and 12 rocks, and trace ferric iron in lunar and meteoritic titanaugites.

Hapke, B.↗
NASA NTRS1972

Investigation of a possible solar-wind darkening of the lunar surface by photoelectron spectroscopy.

Detailed sequential study by photoelectron spectroscopy of the change in valence states of iron in Fe2O3, Fe3O4, FeO, and Fe foil samples, showing that chemical reduction does take place on the sample surface when argon ion bombardment occurs. These spectra give evidence that, after prolonged ion bombardment, the surface of all four samples consisted predominantly of iron in the metallic state. Argon ion sputtering of 15 silicate and oxide samples under similar experimental conditions produced surface darkening only in samples containing iron. Monitoring of the photoelectron peak of carbon during the experiment indicates that ion-bombardment darkening is not due to the buildup of hydrocarbon surface contaminants in the oil-free high-vacuum system used by the authors. On the basis of these studies, it is concluded that solar-wind bombardment should be included as one of the possible mechanisms for producing darkening of the lunar surface.

Yin, L. I.↗
NASA NTRS1972

Indium.

The abundances of indium in the cosmos, meteorites, and tektites, in rock-forming and ore minerals, and in common igneous rocks are tabulated, with brief comments. Indium's behavior in magmatogenic processes and during weathering and alteration of rocks is described. Attention is given to solubilities of compounds, adsorption processes, and valence states. Also tabulated are the abundances in common sediments and in sedimentary and metamorphic rocks.

Linn, T. A., Jr.↗
NASA NTRS1975

Electron spectroscopic studies related to solar-wind darkening of the lunar surface

Improved instrumentation in the X-ray photoelectron spectrometer allowed the first direct observation of the change of valence state of iron in the silicate Fayalite under helium-ion bombardment. From the observed ion dosage necessary to reduce the iron in the topmost atomic layers to the metallic state it is estimated that similar reduction on the lunar surface under solar-wind proton bombardment would occur between 700 to 1000 years. Within such a time scale, it seems likely that all surface iron in the iron-containing lunar fines should have been reduced to the metallic state. Implications of these experimental observations in terms of various proposed darkening mechanisms are discussed.

Yin, L. I.↗