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Full CI benchmark calculations for several states of the same symmetry

Full CI (FCI) wave functions are used to compute energies for several electronic states of the same symmetry for SiH2, CH2, and CH2(+). It is found that CASSCF/multireference CI wave functions yield results very similar to FCI, irrespective of whether the CASSCF MOs are optimized independently for each state or using an average of the CASSCF energies for all desired states. The ionization potentials and excitation energies obtained from the FCI calculations should help calibrate methods (such as Green's function approaches, equations of motion and propagator methods, and cluster expansions) in which energy differences are computed directly.

Bauschlicher, Charles W., Jr.↗

Carbonates and sulfates in CI chondrites - Formation by aqueous activity on the parent body

Compositions and morphologies of dolomites, breunnerites, Ca-carbonates, Ca-sulfates and Mg, Ni, Na-sulfates, and their petrologic interrelations, in four CI chondrites are consistent with their having been formed by aqueous activity on the CI parent body. Radiochronometric data indicate that this activity took place very early in solar-system history. No evidence for original ('primitive') condensates seems to be present. However, alteration apparently took place without change in bulk meteorite composition.

Fredriksson, Kurt↗

Volatiles in interplanetary dust particles: A comparison with CI and CM chondrites

In an effort to classify and determine the origin of interplanetary dust particles (IDPs), 14 of these particles were studied using a laser microprobe/mass spectrometer. The mass spectra for these particles varied dramatically. Some particles released hydroxide or water which probably originated in hydroxide-bearing minerals or hydrates. Others produced spectra which included a number of hydrocarbons and resembled meteorite spectra. However, none of the individual IDPs gave spectra which could be matched identically with a particular meteorite type such as a CI or CM carbonaceous chondrite. We believe this was due to the fact that 10-20 micron size IDPs are too small to be representative of the parent body. To verify that the diversity was due primarily to the small particle sizes, small grains of approximately the same size range as the IDPs were obtained from two primitive meteorites, Murchison and Orgueil, and these small meteorite particles were treated exactly like the IDPs. Considerable diversity was observed among individual grains, but a composite spectrum of all the grains from one meteorite closely resembled the spectrum obtained from a much larger sample of that meteorite. A composite spectrum of the 14 IDPs also resembled the spectra of the CM and CI meteorites, pointing to a possible link between IDPs and carbonaceous chondrites. This also illustrates that despite the inherent diversity in particles as small as 10-20 micron, conclusions can be drawn about the possible origin and overall composition of such particles by looking not only at results from individual particles but also by including many particles in a study and basing conclusions on some kind of composite data.

Bustin, Roberta↗

Petrologic study of the Belgica 7904 carbonaceous chondrite - Hydrous alteration, oxygen isotopes, and relationship to CM and CI chondrites

The genetic relationships between the petrology, hydration reactions, and isotopic oxygen composition in the Belgica 7904 (B7904) carbonaceous chondrite, and the relationship between B7904 and the CM and CI chondrites were investigated by characterizing seven components separated from B7904. The seven specimens included two partially altered chondrules, two phylosilicate clasts, two olivine fragments, and one matrix sample. The results of the analyses and thermodynamic calculations suggest that CI chondrites may have been produced in a two-stage alteration process from materials similar to that of the B7904 matrix, by reactions with liquid water in their parent body. The common CM chondrites may have undergone aqueous alteration in the parent body, in addition to hydration in the nebula, resulting in two-stage alterations; the parent body may have been different from that of B7904.

Ikeda, Y.↗

Comment on Mars as the Parent Body of the CI Carbonaceous Chondrites by J. E. Brandenburg

Geological and chemical data refute a martian origin for the CI carbonaceous chondrites. Here, I will first consider Brandenburg's [1996] proposal that the CI's formed as water-deposited sediments on Mars, and that these sediments had limited chemical interactions with their martian environment. Finally, I will address oxygen isotope ratios, the strongest link between the CIs and the martian meteorites.

Treiman, Allan H.↗

Metamorphosed CM and CI Carbonaceous Chondrites Could Be from the Breakup of the Same Earth-crossing Asteroid

Far from being the relatively unprocessed materials they were once believed to be, we now know that a significant number of carbonaceous chondrites were thermally metamorphosed on their parent asteroid(s). Numerous studies indicate that 7 "CM" and 2 "CI" chondrites have been naturally heated, variously, at from 400 to over 700 C on their parent asteroid(s). Petrographic textures reveal that this thermal metamorphism occurred after the dominant aqueous alteration phase, although some meteorites show evidence of a heating event between two aqueous alteration episodes, i.e. pro- and retrograde aqueous alteration. Aside from the issues of the identification of the transient heat source, timing of metamorphism, and the relation of these materials (if any) to conventional CM and CI chondrites, there is also a mystery related to their recovery. All of these meteorites have been recovered from the Antarctic; none are falls or finds from anyplace else. Indeed, the majority have been collected by the Japanese NIPR field parties in the Yamato Mountains. In fact, one estimate is that these meteorites account for approx. 64 wt% of the CM carbonaceous chondrites at the NIPR. The reasons for this are unclear and might be due in part to simple sampling bias. However we suggest that this recovery difference is related to the particular age of the Yamato Mountains meteorite recovery surfaces, and differences in meteoroid fluxes between the Yamato meteorites and recent falls and substantially older Antarctic meteorites. Additional information is included in the original extended abstract.

Zolensky, Michael↗

Surviving High-temperature Components in CI Chondrites

The CI1 chondrites, while having the most solar-like compo-sition of any astromaterial available for laboratory analysis, have also been considerably altered by asteroidal processes including aqueous alteration. It is of fundamental importance to determine their pre-alteration mineralogy, so that the state of matter in the early Solar System can be better determined. In the course of a re-examination of the compositional range of olivine and low-Ca pyroxene in CI chondrites Orgueil, Ivuna and Alais [1] we found the first reported complete CAI, as already reported [2], with at-tached rock consisting mainly of olivine and low-Ca pyroxene. The range of residual olivine major element compositions we have determined in the CIs (Fig. 1) may now be directly com-pared with those of other astromaterials, including Wild 2 grains. The abundance of olivine and low-Ca pyroxene in CIs is higher than is generally appreciated, and in fact much higher than for some CMs [1]. We also noted numerous rounded objects varying in shape from spheres to oblate spheroids, and ranging up to 100μm in size (Fig. 2), which have been previously noted [3] but have not been well documented or appreciated. We characterized the mineralogy by transmission electron microscopy and found that they consist mainly of rather fine-grained, flaky single phase to intergrown serpentine and saponite. These two materials in fact dominate the bulk of the host CI1 chondrites. With the exception of sparse spinels, the rounded phyllosilicate objects are remarka-bly free of other minerals, suggesting that the precursor from which the phyllosilicates were derived was a homogeneous mate-rial. We suggest that these round phyllosilicates aggregates in CI1 chondrites were cryptocrystalline to glassy microchondrules. If so then CI chondrites cannot be considered chondrule-free. Small though they are, the abundance of these putative microchondrules is the same as that of chondrules in the Tagish Lake meteorite.

Zolensky, M.↗

Oxygen Isotope Ratios of Magnetite in CI-Like Clasts from a Polymict Ureilite

Polymict ureilites contain a variety of Less than or equal to mm to cm sized non-ureilitic clasts, many of which can be identifed as chondritic and achondritic meteorite types. Among them, dark clasts have been observed in polymict ureilites that are similar to CI chondrites in mineralogy, containing phyllosilicates, magnetite, sulfide and carbonates. Bulk oxygen isotope analyses of a dark clast in Nilpena plot along the CCAM line and above the terrestrial fractionation line, on the O-poor extension of the main group ureilite trend and clearly different from bulk CI chondrites. One possible origins of such dark clast is that they represent aqueously altered precursors of ureilite parent body (UPB) that were preserved on the cold surface of the UPB. Oxygen isotope analyses of dark clasts are key to better understanding their origins. Oxygen isotope ratios of magnetite are of special interest because they reflect the compositions of the fluids in asteroidal bodies. In primitive chondrites, Delta O (= Delta O - 0.52× Delta O) values of magnetites are always higher than those of the bulk meteorites and represent minimum Delta O values of the initial O-poor aqueous fluids in the parent body. Previous SIMS analyses on magnetite and fayalite in dark clasts from the DaG 319 polymict ureilite were analytically difficult due to small grain sizes, though data indicated positive Delta O values of 3-4 per mille, higher than that of the dark clast in Nilpena (1.49per mille).

Kita, N. T.↗

Olivine Mineralogy of Asteroid Ryugu Samples and CI Chondrites: Further Evidence for their Common Origin

Initial analysis of asteroid Ryugu samples has revealed that they were mm-mm scale brecciamostly composed of aqueously altered phases (e.g., Mg-Fe phyllosilicates, carbonates) and showed remarkablesimilarities to CI chondrites in mineralogy and chemistry [e.g., 1,2]. Our detailed analysis of Ryugu samples hasdetected small amounts (<<1 vol.%) of unaltered silicates that would escape severe aqueous alteration [3]. Olivine isthe most abundant (>90 vol%) phase among such unaltered silicates. Although most Ryugu olivine grains aresmaller than 5 mm, they bear important information about the precursors of the parent Ryugu asteroid. In thisabstract we report additional results of olivine mineralogical study of Ryugu samples, and especially compare witholivine grains in CI chondrites (Ivuna and Orgueil) to further discuss their relationship and possible common origin.

T. Mikouchi↗

Less-Altered CI Lithology in the Kaidun Meteorite Breccia

One of the most interesting initial results of the characterization of the asteroid Ryugu regolith material returned by the Hayabusa2 spacecraft is the presence of a significant quantity of less-aqueously altered CI material, tentatively called “CI2”. This lithology is characterized by an approximately ten-fold increase in the amount of an hydrous ferromagnesian silicates over what is found n CI1 chondrites, with these being principally olivine, low- and high-calcium pyroxene. Remnant CAI phases are found as well as probable chondrule fragments. Magnetite, pyrrhotite and hydroxyapatite are abundant. The main carbonate is calcite. Matrix is mainly a mixture of saponite and serpentine phases. Assuming that this lithology should be a better representative of the more “primordial” mineralogy of early nebular solids than more processed CI1 material, we have been re-examining CI lithologies found as separate meteorites as well as clasts in other meteorites, seeking similar CI2 material. The Kaidun breccia is notorious for including almost every type of meteorite class except CR2 (which is ironic considering that Kaidun is still officially classified as CR2). We report here the discovery of a probable CI2 lithology in one carbonaceous chondrite-rich Kaidun sample.

Michael Zolensky↗

Olivine Compositional Systematics of CI Chondrites and Asteroid Ryugu

Recent findings of rare anhydrous silicates (especially, olivine) in asteroid Ryugu samples suggest that small amounts of precursor materials escaped subsequent aqueous alteration in the Ryugu parent body [e.g., 1]. The origins of these anhydrous grains are considered to be either AOA-like or chondrule-like materials [2,3]. We have studied CI chondrites Ivuna and Orgueil on the same manner to analyze Ryugu samples and found the similar occurrence of anhydrous silicates in these brecciated meteorites [4]. In this abstract we report the mineralogy of olivine grains in another CI chondrite Alais to compare with Orgueil and Ivuna as well as Ryugu samples to better understand their origins through compositional systematics obtained by detailed FE-EPMA analysis.

T. Mikouchi↗

Materials Data on SnH8(CI)4 by Materials Project

SnH8(CI)4 is Protactinium structured and crystallizes in the tetragonal P-42_1c space group. The structure is zero-dimensional and consists of two stannane, tetrakis(iodomethyl)- molecules. Sn4+ is bonded in a tetrahedral geometry to four equivalent C2- atoms. All Sn–C bond lengths are 2.17 Å. C2- is bonded in a 2-coordinate geometry to one Sn4+, two H1+, and one I1- atom. There is one shorter (1.09 Å) and one longer (1.10 Å) C–H bond length. The C–I bond length is 2.16 Å. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one C2- atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one C2- atom. I1- is bonded in a single-bond geometry to one C2- atom.

36 MATERIALS SCIENCE↗

Materials Data on SiH8(CI)4 by Materials Project

SiH8(CI)4 is Protactinium-like structured and crystallizes in the orthorhombic P2_12_12_1 space group. The structure is zero-dimensional and consists of eight tetrakis(iodomethyl)silane molecules.

36 MATERIALS SCIENCE↗

CI-MBPT and Intensity-Based Lifetime Calculations for Th II

Lifetime calculations of Th II J = 1.5 and 2.5 odd states are performed with configuration–interaction many-body perturbation theory (CI-MBPT). For many J = 2.5 states, lifetimes are quite accurate, but two pairs of J = 2.5 odd states and many groups of J = 1.5 states are strongly mixed, making theoretical predictions unreliable. To solve this problem, a method based on intensities is used. To relate experimental intensities to lifetimes, two parameters, one an overall coefficient of proportionality for transition rates and one temperature of the Boltzmann distribution of populations, are introduced and fitted to minimize the deviation between theoretical and intensity-derived lifetimes. For strongly mixed groups of states, the averaged lifetimes obtained from averaged transition rates were used instead of individual lifetimes in the fit. Close agreement is obtained. Then intensity branching ratios are used to extract individual lifetimes for the strongly mixed states. The resulting lifetimes are compared to available directly measured lifetimes and reasonable agreement is found, considering limited accuracy of intensity measurements. The method of intensity-based lifetime calculations with fit to theoretical lifetimes is quite general and can be applied to many complex atoms where strong mixing between multiple states exists.

74 ATOMIC AND MOLECULAR PHYSICS↗

Experimental Investigation of the Effect of Air-Handling and DME-Propane Blends on the Performance and Emissions of a 4-Cylinder CI Engine

Dimethyl ether (DME) is considered an excellent alternative to diesel because of its higher cetane number and lower carbon content. Additionally, DME can be blended with abundantly available propane with minimal modifications to the propane infrastructure. This paper focuses on an experimental investigation of the effect of air-handling i.e., boost pressure and exhaust gas recirculation (EGR), and DME-propane blends on the combustion and emissions performance of a light-duty, four-cylinder, compression ignition (CI) engine. Here, the boost pressure and EGR sweeps were carried out and showed that higher boost pressures resulted in increased brake thermal efficiencies (BTE) at the expense of higher NOx emissions which could be reduced by an increase in EGR. The fuel sweeps were carried out at 0, 15 and 25% propane (neat, 85% and 75% DME) with 0% and 25% EGR. The fuel sweeps indicated that the ignition delay (ID) increased and burn duration (BD) decreased monotonically when the blend increased to 25% propane/75% DME. The results suggest optimum engine performance with neat DME at 105 kPa boost pressure and 25% EGR with propane addition improving the BTE with negligible increase in emissions. Higher contents of Propane, up to 25%, did not affect the variability of combustion, with standard deviations of burn duration and peak cylinder pressures below 1% for all test cases.

air-handling↗

Rb-Sr studies of CI and CM chondrites

Rb-Sr whole rock analyses have been performed on 2 CI and 3 CM chondrites. Four of these stones (Ivuna, Orgueil, Cold Bokkeveld and Erakot) were previously studied in this laboratory and were shown to be discordant from a 4.6 Gyr isochron. The fifth, Murchison, was not previously studied. The new data support the discordance of the first four stones, and indicate that Murchison is also discordant. Studies of Sr isotope ratios in unspiked Orgueil show that the discordance is not due to inhomogeneities in the Sr-84/Sr-86 ratio caused by incomplete mixing of nucleosynthesis products. In order to gauge the effects of weathering, two leaching experiments were performed on fresh, interior samples of Murchison; one for a period of 1.5 hr and the other for 117 hr. The results indicate that the relative solubility of nonradiogenic Sr is approximately twice that of Rb and radiogenic Sr is more soluble than the nonradiogenic Sr.

Mittlefehldt, D. W.↗