The geochronology of the plutonic and metamorphic rocks of New Zealand

Extensive Rubidium-Strontium age determinations on both mineral and total rock samples of the crystalline rocks of New Zealand, which almost solely crop out in the South Island, indicate widespread plutonic and metamorphic activity occurred during two periods, one about 100-118 million years ago and the other about 340-370 million years ago. The former results date the Rangitata Orogeny as Cretaceous. They associate extensive plutonic activity with this orogeny which uplifted and metamorphosed the rocks of the New Zealand Geosyncline, although no field association between the metamorphosed geosynclinal rocks and plutonic rocks has been found. The Cretaceous plutonic rocks occur to the west in the Foreland Province in Fiordland, Nelson, and Westland, geographically separated from the Geosynclinal Province. Because of this synchronous timing of plutonic and high pressure metamorphic activity in spatially separated belts, the Rangitata Orogeny in New Zealand is very similar to late Mesozoic orogenic activity in many other areas of the circum-Pacific margin (Miyashiro, 1961).

The 340-370 million year rocks, both plutonic and metamorphic, have been found only in that part of the Foreland Province north of the Alpine Fault. There, they are concentrated along the west coast over a distance of 500 km, and appear scattered inland from the coast. Probably this activity marks the outstanding Phanerozoic stratigraphic gap in New Zealand which occurred after the Lower Devonian.

A few crystalline rocks in the Foreland Province north of the Alpine Fault with measured ages intermediate between 340 and 120 million years have been found. Of these, those with more than one mineral examined give discordant results. All of these rocks are tentatively regarded as 340-370 million year old rocks that have been variously disturbed during the Rangitata Orogeny, 100-120 million years ago.

In addition to these two periods, plutonic activity, dominantly basic and ultrabasic, but including the development of some rocks of intermediate and acidic composition, occurred along the margin of the Geosynclinal Province at its border with the Foreland Province during Permian times about 245 million years ago, and this activity possibly extended into the Mesozoic.

Evidence from rubidium-strontium analyses of minerals and a total rock, and from uranium, thorium, and lead analyses of uniform euhedral zircons from a meta-igneous portion of the Charleston Gneiss, previously mapped as Precambrian, indicate that this rock is a 350-370 million year old plutonic rock metamorphosed 100 million yea rs ago during the Rangitata Orogeny. No crystalline rocks with primary Precambrian ages have been found in New Zealand. However, Pb²⁰⁷/Pb₂₀₆ ages of 1360 million years and 1370 million years have been determined for rounded detrital zircons separated from each of two hornfels samples of one of New Zealand's olde st sedimentary units, the Greenland Series. These two samples were metamorphosed 345- 370 million years ago. They occur along the west coast, north of the Alpine Fault, at Waitaha River and Moeraki River, separated by 135 km. The Precambrian measured ages are most likely minimum ages for the oldest source area which provided the detrital zircons because the uranium, thorium and lead data are highly discordant. These results are of fundamental importance for the tectonic picture of the Southwest Pacific margin and demonstrate the existence of relatively old continental crust of some lateral extent in the neighborhood of New Zealand.

Seismic reflection experiments imaging the physical nature of crustal structures in southern California

Seismic reflection methods have been extensively used to probe the Earth's crust and suggest the nature of its formative processes. The analysis of multi-offset seismic reflection data extends the technique from a reconnaissance method to a powerful scientific tool that can be applied to test specific hypotheses. The treatment of reflections at multiple offsets becomes tractable if the assumptions of high-frequency rays are valid for the problem being considered. Their validity can be tested by applying the methods of analysis to full wave synthetics.

Three studies illustrate the application of these principles to investigations of the nature of the crust in southern California. A survey shot by the COCORP consortium in 1977 across the San Andreas fault near Parkfield revealed events in the record sections whose arrival time decreased with offset. The reflectors generating these events are imaged using a multi-offset three-dimensional Kirchhoff migration. Migrations of full wave acoustic synthetics having the same limitations in geometric coverage as the field survey demonstrate the utility of this back projection process for imaging. The migrated depth sections show the locations of the major physical boundaries of the San Andreas fault zone. The zone is bounded on the southwest by a near-vertical fault juxtaposing a Tertiary sedimentary section against uplifted crystalline rocks of the fault zone block. On the northeast, the fault zone is bounded by a fault dipping into the San Andreas, which includes slices of serpentinized ultramafics, intersecting it at 3 km depth. These interpretations can be made despite complications introduced by lateral heterogeneities.

In 1985 the Calcrust consortium designed a survey in the eastern Mojave desert to image structures in both the shallow and the deep crust. Preliminary field experiments showed that the major geophysical acquisition problem to be solved was the poor penetration of seismic energy through a low-velocity surface layer. Its effects could be mitigated through special acquisition and processing techniques. Data obtained from industry showed that quality data could be obtained from areas having a deeper, older sedimentary cover, causing a re-definition of the geologic objectives. Long offset stationary arrays were designed to provide reversed, wider angle coverage of the deep crust over parts of the survey. The preliminary field tests and constant monitoring of data quality and parameter adjustment allowed 108 km of excellent crustal data to be obtained.

This dataset, along with two others from the central and western Mojave, was used to constrain rock properties and the physical condition of the crust. The multi-offset analysis proceeded in two steps. First, an increase in reflection peak frequency with offset is indicative of a thinly layered reflector. The thickness and velocity contrast of the layering can be calculated from the spectral dispersion, to discriminate between structures resulting from broad scale or local effects. Second, the amplitude effects at different offsets of P-P scattering from weak elastic heterogeneities indicate whether the signs of the changes in density, rigidity, and Lame's parameter at the reflector agree or are opposed. The effects of reflection generation and propagation in a heterogeneous, anisotropic crust were contained by the design of the experiment and the simplicity of the observed amplitude and frequency trends. Multi-offset spectra and amplitude trend stacks of the three Mojave Desert datasets suggest that the most reflective structures in the middle crust are strong Poisson's ratio (σ) contrasts. Porous zones or the juxtaposition of units of mutually distant origin are indicated. Heterogeneities in σ increase towards the top of a basal crustal zone at ~22 km depth. The transition to the basal zone and to the mantle include increases in σ. The Moho itself includes ~400 m layering having a velocity higher than that of the uppermost mantle. The Moho maintains the same configuration across the Mojave despite 5 km of crustal thinning near the Colorado River. This indicates that Miocene extension there either thinned just the basal zone, or that the basal zone developed regionally after the extensional event.

Identifying and interpreting stratification in sedimentary rocks on Mars : insight from Rover and orbital observations and terrestrial field analogs

Sedimentary rocks on Mars provide insight into past aqueous and atmospheric processes, climate regimes, and potential habitability. The stratigraphic architecture of sedimentary rocks on Mars is similar to that of Earth, indicating that the processes that govern deposition and erosion on Mars can be reasonably inferred through reference to analogous terrestrial systems. This dissertation aims to understand Martian surface processes through the use of (1) ground-based observations from the Mars Exploration Rovers, (2) orbital data from the High Resolution Imaging Science Experiment onboard the Mars Reconnaissance Orbiter, and (3) the use of terrestrial field analogs to understand bedforms and sediment transport on Mars. Chapters 1 and 2 trace the history of aqueous activity at Meridiani Planum, through the reconstruction of eolian bedforms at Victoria crater, and the identification of a potential mudstone facies at Santa Maria crater. Chapter 3 uses Terrestrial Laser Scanning to study cross-bedding in pyroclastic surge deposits on Earth in order to understand sediment transport in these events and to establish criteria for their identification on Mars. The final chapter analyzes stratal geometries in the Martian North Polar Layered Deposits using tools for sequence stratigraphic analysis, to better constrain past surface processes and past climate conditions on Mars.

Probing the thermodynamic properties of mantle rocks in solid and liquid states

Our understanding of the structure and evolution of the deep Earth is strongly linked to knowledge of the thermodynamic properties of rocky materials at extreme temperatures and pressures. In this thesis, I present work that helps constrain the equation of state properties of iron-bearing Mg-silicate perovskite as well as oxide-silicate melts. I use a mixture of experimental, statistical, and theoretical techniques to obtain knowledge about these phases. These include laser-heated diamond anvil cell experiments, Bayesian statistical analysis of powder diffraction data, and the development of a new simplified model for understanding oxide and silicate melts at mantle conditions. By shedding light on the thermodynamic properties of such ubiquitous Earth-forming materials, I hope to aid our community’s progress toward understanding the large-scale processes operating in the Earth’s mantle, both in the modern day and early in Earth’s history.

I. Impact spallation experiments: fracture patterns and spall velocities. II. Craters in carbonate rocks: an electron paramagnetic resonance analysis of shock damage

This work is divided into two independent papers.

PAPER 1.

Spall velocities were measured for nine experimental impacts into San Marcos gabbro targets. Impact velocities ranged from 1 to 6.5 km/sec. Projectiles were iron, aluminum, lead, and basalt of varying sizes. The projectile masses ranged from a 4 g lead bullet to a 0.04 g aluminum sphere. The velocities of fragments were measured from high-speed films taken of the events. The maximum spall velocity observed was 30 m/sec, or 0.56 percent of the 5.4 km/sec impact velocity. The measured velocities were compared to the spall velocities predicted by the spallation model of Melosh (1984). The compatibility between the spallation model for large planetary impacts and the results of these small scale experiments are considered in detail.

The targets were also bisected to observe the pattern of internal fractures. A series of fractures were observed, whose location coincided with the boundary between rock subjected to the peak shock compression and a theoretical "near surface zone" predicted by the spallation model. Thus, between this boundary and the free surface, the target material should receive reduced levels of compressive stress as compared to the more highly shocked region below.

PAPER 2.

Carbonate samples from the nuclear explosion crater, OAK, and a terrestrial impact crater, Meteor Crater, were analyzed for shock damage using electron para- magnetic resonance, EPR. The first series of samples for OAK Crater were obtained from six boreholes within the crater, and the second series were ejecta samples recovered from the crater floor. The degree of shock damage in the carbonate material was assessed by comparing the sample spectra to spectra of Solenhofen limestone, which had been shocked to known pressures.

The results of the OAK borehole analysis have identified a thin zone of highly shocked carbonate material underneath the crater floor. This zone has a maximum depth of approximately 200 ft below sea floor at the ground zero borehole and decreases in depth towards the crater rim. A layer of highly shocked material is also found on the surface in the vicinity of the reference bolehole, located outside the crater. This material could represent a fallout layer. The ejecta samples have experienced a range of shock pressures.

It was also demonstrated that the EPR technique is feasible for the study of terrestrial impact craters formed in carbonate bedrock. The results for the Meteor Crater analysis suggest a slight degree of shock damage present in the β member of the Kaibab Formation exposed in the crater walls.

^(18)O/^(16)O and D/H studies on the interactions between heated meteoric ground waters and igneous intrusions: Western San Juan Mountains, Colorado and the Isle of Skye, Scotland

Detailed oxygen, hydrogen and carbon isotope studies have been carried out on igneous and metamorphic rocks of the Stony Mountain complex, Colorado, and the Isle of Skye, Scotland, in order to better understand the problems of hydrothermal meteoric water-rock interaction.

The Tertiary Stony Mountain stock (~1.3 km in diameter), is composed of an outer diorite, a main mass of biotite gabbro, and an inner diorite. The entire complex and most of the surrounding country rocks have experienced various degrees of ¹⁸O depletion (up to 10 per mil) due to interaction with heated meteoric waters. The inner diorite apparently formed from a low-¹⁸O magma with δ¹⁸O ≃ +2.5, but most of the isotopic effects are a result of exchange between H₂O and solidified igneous rocks. The low-¹⁸O inner diorite magma was probably produced by massive assimilation and/or melting of hydrothermally altered country rocks. The δ¹⁸O values of the rocks generally increase with increasing grain size, except that quartz typically has δ¹⁸O = +6 to +8, and is more resistant to hydrothermal exchange than any other mineral studied. Based on atom % oxygen, the outer diorites, gabbros, and volcanic rocks exhibit integrated water/rock ratios of 0.3 ± 0.2, 0.15 ± 0.1, and 0.2 ± 0.1, respectively. Locally, water/rock ratios attain values greater than 1.0. Hydrogen isotopic analyses of sericites, chlorites, biotites, and amphiboles range from -117 to -150. δD in biotites varies inversely with Fe/Fe+Mg, as predicted by Suzuoki and Epstein (1974), and positively with elevation, over a range of 600 m. The calculated δD of the mid-to-late-Tertiary meteoric waters is about -100. Carbonate δ¹³C values average -5.5 (PDB), within the generally accepted range for deep-seated carbon.

Almost all the rocks within 4 km of the central Tertiary intrusive complex of Skye are depleted in ¹⁸O. Whole-rock δ¹⁸O values of basalts (-7. 1 to +8.4), Mesozoic shales (-0.6 to + 12.4), and Precambrian sandstones (-6.2 to + 10.8) systematically decrease inward towards the center of the complex. The Cuillin gabbro may have formed from a ¹⁸O-depleted magma (depleted by about 2 per mil); δ¹⁸O of plagioclase (-7.1 to + 2.5) and pyroxene (-0.5 to + 3.2) decrease outward toward the margins of the pluton. The Red Hills epigranite plutons have δ¹⁸O quartz (-2.7 to + 7.6) and feldspar (-6.7 to + 6.0) that suggest about 3/4 of the exchange took place at subsolidus temperatures; profound disequilibrium quartz-feldspar fractionations (up to 12) are characteristic. The early epigranites were intruded as low-¹⁸O melts (depletions of up to 3 per mil) with δ¹⁸O of the primary, igneous quartz decreasing progressively with time. The Southern Porphyritic Epigranite was apparently intruded as a low-¹⁸O magma with δ¹⁸O ≃ -2.6. A good correlation exists between grain size and δ¹⁸O for the unique, high-¹⁸O Beinn an Dubhaich granite which intrudes limestone having a δ¹⁸O range of +0.5 to +20.8, and δ¹³C of -4.9 to -1.0. The δD values of sericites (-104 to -107), and amphiboles, chlorites, and biotites (-105 to -128) from the igneous rocks , indicate that Eocene surface waters at Skye had δD ≃ -90. The average water/rock ratio for the Skye hydrothermal system is approximately one; at least 2000 km³ of heated meteoric waters were cycled through these rocks.

Thus these detailed isotopic studies of two widely separated areas indicate that (1) ¹⁸O-depleted magmas are commonly produced in volcanic terranes invaded by epizonal intrusions; (2) most of the ¹⁸O-depletion in such areas are a result of subsolidus exchange (particularly of feldspars); however correlation of δ¹⁸O with grain size is generally preserved only for systems that have undergone relatively minor meteoric hydrothermal exchange; (3) feldspar and calcite are the minerals mos t susceptible to oxygen isotopic exchange, whereas quartz is very resistant to oxygen isotope exchange; biotite, magnetite, and pyroxene have intermediate susceptibilities; and (4) basaltic country rocks are much more permeable to the hydrothermal convective system than shale, sandstone, or the crystalline basement complex.

The structure and petrology of the Johnny Lyon Hills area, Cochise County, Arizona

The Johnny Lyon Hills area is located in Cochise County in southeastern Arizona. The rocks of the area include a central core of Lower pre-Cambrian igneous and metamorphic rocks surrounded by a complexly faulted and tilted section of Upper pre-Cambrian and Paleozoic strata. Limited exposures of Mesozoic and Tertiary sedimentary and volcanic rocks are present at the north end of the map area. Late Tertiary and Quaternary alluvium almost completely surrounds and overlaps upon the older rocks.

The older pre-Cambrian rocks include a section of more than 9000 feet of generally moderately metamorphosed graywackes, slates and conglomerates of the Pinal schist injected in zones by somewhat younger rnyolite sheets. The original sediments were deposited in a geosyncline whose extent probably included large parts of Arizona, New Mexico and west Texas. During the Mazatzal Revolution the Pinal schist was deformed into northeast-trending, steeply dipping and plunging structures and the entire local section was overturned steeply toward the northwest. The pre-Cambrian Johnny Lyon granodiorite was emplaced as a large epi-tectonic pluton which modified the metamorphic character of part of the Pinal schist. Larsen method determinations indicate an age of about 715 million years for this rock, which is about the minimum age compatible with the geologic relations.

The Laramide orogeny produced numerous major thrust faults in the area involving all rocks older than and including the Lower Cretaceous Bisbee group. Major compression from the southwest and subsequent superimposed thrusting from the southeast and east are indicated. Minimum thrust displacements of more than a mile are clear and the probable displacements are of much greater magnitude. The crystalline core behaved as a single structural unit and probably caused important local divergences from the regional pattern of northeast-trending compressive forces. The massif was rotated as a unit 40 degrees or more about a northwest-trending axis overturning the pre-Cambrian fold axes in the Pinal schist.

Swarms of Late Cretaceous(?) or Early Tertiary(?) lamprophyric dikes cross the Laramide structures and are probably related to the large Texas Canyon stock several miles southeast of the map area. Intermittent high angle faulting, both older and younger than the dikes, has continued since the Laramide orogeny and has been superimposed on the older structures. This steep faulting combined with the fundamental northwesterly Laramide structural grain to produce the northwesterly trends characteristic of the mountain ridges and valleys of the area.

Oxygen isotope ratios in coexisting minerals of regionally metamorphosed rocks

The O¹⁸/O¹⁶ ratios of coexisting minerals from a number of regionally metamorphosed rocks have been measured, using a bromine pentafluoride extraction-technique. Listed in order of their increasing tendency to concentrate O¹⁸, the minerals analyzed are magnetite, ilmenite, chlorite, biotite, garnet, hornblende, kyanite, muscovite, feldspar, and quartz. The only anomalous sequence detected occurs in a xenolith of schist, in which quartz, muscovite, biotite, and ilmenite, but not garnet, have undergone isotopic exchange with surrounding trondjemite.

With few exceptions, quartz-magnetite and quartz-ilmenite fractionations decrease with increasing metamorphic grade determined by mineral paragenesis and spatial distribution. This consistency does not apply to quartz-magnetite and quartz-ilmenite fractionations obtained from rocks in which petrographic evidence of retrogradation is present.

Whereas measured isotopic fractionations among quartz, garnet, ilmenite, and magnetite are approximately related to metamorphic grade, fractionations between these minerals and biotite or muscovite show poor correlation with grade. Variations in muscovite-biotite fractionations are relatively small. These observations are interpreted to mean that muscovite and biotite are affected by retrograde re-equilibration to a greater extent than the anhydrous minerals analyzed.

Measured quartz-ilmenite fractionations range from 12 permil in the biotite zone of central Vermont to 6.5 permil in the sillimanite-orthoclase zone of southeastern Connecticut. Analyses of natural assemblages from the kyanite and sillimanite zones suggest that equilibrium quartz-ilmenite fractionations are approximately 8 percent smaller than corresponding quartz-magnetite fractionations. Employing the quartz-magnetite geothermometer calibrated by O'Neil and Clayton (1964), a temperature of 560°C was obtained for kyanite-bearing schists from Addison County, Vermont. Extending the calibration to quartz-ilmenite fractionations, a temperature of 600°C was obtained for kyanite-schists from Shoshone County, Idaho. At these temperatures kyanite is stable only at pressures exceeding 11 kbars (Bell, 1963), corresponding to lithostatic loads of over 40 km.

I. The Superstition Hills, California, earthquakes of 24 November 1987. II. Three-dimensional velocity structure of southern California.

Part 1 of this thesis is about the 24 November, 1987, Superstition Hills earthquakes. The Superstition Hills earthquakes occurred in the western Imperial Valley in southern California. The earthquakes took place on a conjugate fault system consisting of the northwest-striking right-lateral Superstition Hills fault and a previously unknown Elmore Ranch fault, a northeast-striking left-lateral structure defined by surface rupture and a lineation of hypocenters. The earthquake sequence consisted of foreshocks, the M_s 6.2 first main shock, and aftershocks on the Elmore Ranch fault followed by the M_s 6.6 second main shock and aftershocks on the Superstition Hills fault. There was dramatic surface rupture along the Superstition Hills fault in three segments: the northern segment, the southern segment, and the Wienert fault.

In Chapter 2, M_L≥4.0 earthquakes from 1945 to 1971 that have Caltech catalog locations near the 1987 sequence are relocated. It is found that none of the relocated earthquakes occur on the southern segment of the Superstition Hills fault and many occur at the intersection of the Superstition Hills and Elmore Ranch faults. Also, some other northeast-striking faults may have been active during that time.

Chapter 3 discusses the Superstition Hills earthquake sequence using data from the Caltech-U.S.G.S. southern California seismic array. The earthquakes are relocated and their distribution correlated to the type and arrangement of the basement rocks. The larger earthquakes occur only where continental crystalline basement rocks are present. The northern segment of the Superstition Hills fault has more aftershocks than the southern segment.

An inversion of long period teleseismic data of the second mainshock of the 1987 sequence, along the Superstition Hills fault, is done in Chapter 4. Most of the long period seismic energy seen teleseismically is radiated from the southern segment of the Superstition Hills fault. The fault dip is near vertical along the northern segment of the fault and steeply southwest dipping along the southern segment of the fault.

Chapter 5 is a field study of slip and afterslip measurements made along the Superstition Hills fault following the second mainshock. Slip and afterslip measurements were started only two hours after the earthquake. In some locations, afterslip more than doubled the coseismic slip. The northern and southern segments of the Superstition Hills fault differ in the proportion of coseismic and postseismic slip to the total slip.

The northern segment of the Superstition Hills fault had more aftershocks, more historic earthquakes, released less teleseismic energy, and had a smaller proportion of afterslip to total slip than the southern segment. The boundary between the two segments lies at a step in the basement that separates a deeper metasedimentary basement to the south from a shallower crystalline basement to the north.

Part 2 of the thesis deals with the three-dimensional velocity structure of southern California. In Chapter 7, an a priori three-dimensional crustal velocity model is constructed by partitioning southern California into geologic provinces, with each province having a consistent one-dimensional velocity structure. The one-dimensional velocity structures of each region were then assembled into a three-dimensional model. The three-dimension model was calibrated by forward modeling of explosion travel times.

In Chapter 8, the three-dimensional velocity model is used to locate earthquakes. For about 1000 earthquakes relocated in the Los Angeles basin, the three-dimensional model has a variance of the the travel time residuals 47 per cent less than the catalog locations found using a standard one-dimensional velocity model. Other than the 1987 Whittier earthquake sequence, little correspondence is seen between these earthquake locations and elements of a recent structural cross section of the Los Angeles basin. The Whittier sequence involved rupture of a north dipping thrust fault bounded on at least one side by a strike-slip fault. The 1988 Pasadena earthquake was deep left-lateral event on the Raymond fault. The 1989 Montebello earthquake was a thrust event on a structure similar to that on which the Whittier earthquake occurred. The 1989 Malibu earthquake was a thrust or oblique slip event adjacent to the 1979 Malibu earthquake.

At least two of the largest recent thrust earthquakes (San Fernando and Whittier) in the Los Angeles basin have had the extent of their thrust plane ruptures limited by strike-slip faults. This suggests that the buried thrust faults underlying the Los Angeles basin are segmented by strike-slip faults.

Earthquake and explosion travel times are inverted for the three-dimensional velocity structure of southern California in Chapter 9. The inversion reduced the variance of the travel time residuals by 47 per cent compared to the starting model, a reparameterized version of the forward model of Chapter 7. The Los Angeles basin is well resolved, with seismically slow sediments atop a crust of granitic velocities. Moho depth is between 26 and 32 km.

Effect of Microstructural Interfaces on the Mechanical Response of Crystalline Metallic Materials

Advances in nano-scale mechanical testing have brought about progress in the understanding of physical phenomena in materials and a measure of control in the fabrication of novel materials. In contrast to bulk materials that display size-invariant mechanical properties, sub-micron metallic samples show a critical dependence on sample size. The strength of nano-scale single crystalline metals is well-described by a power-law function, σαD^-n, where D is a critical sample size and n is a experimentally-fit positive exponent. This relationship is attributed to source-driven plasticity and demonstrates a strengthening as the decreasing sample size begins to limit the size and number of dislocation sources. A full understanding of this size-dependence is complicated by the presence of microstructural features such as interfaces that can compete with the dominant dislocation-based deformation mechanisms. In this thesis, the effects of microstructural features such as grain boundaries and anisotropic crystallinity on nano-scale metals are investigated through uniaxial compression testing. We find that nano-sized Cu covered by a hard coating displays a Bauschinger effect and the emergence of this behavior can be explained through a simple dislocation-based analytic model. Al nano-pillars containing a single vertically-oriented coincident site lattice grain boundary are found to show similar deformation to single-crystalline nano-pillars with slip traces passing through the grain boundary. With increasing tilt angle of the grain boundary from the pillar axis, we observe a transition from dislocation-dominated deformation to grain boundary sliding. Crystallites are observed to shear along the grain boundary and molecular dynamics simulations reveal a mechanism of atomic migration that accommodates boundary sliding. We conclude with an analysis of the effects of inherent crystal anisotropy and alloying on the mechanical behavior of the Mg alloy, AZ31. Through comparison to pure Mg, we show that the size effect dominates the strength of samples below 10 μm, that differences in the size effect between hexagonal slip systems is due to the inherent crystal anisotropy, suggesting that the fundamental mechanism of the size effect in these slip systems is the same.

A model for energy and morphology of crystalline grain boundaries with arbitrary geometric character

It has been well-established that interfaces in crystalline materials are key players in the mechanics of a variety of mesoscopic processes such as solidification, recrystallization, grain boundary migration, and severe plastic deformation. In particular, interfaces with complex morphologies have been observed to play a crucial role in many micromechanical phenomena such as grain boundary migration, stability, and twinning. Interfaces are a unique type of material defect in that they demonstrate a breadth of behavior and characteristics eluding simplified descriptions. Indeed, modeling the complex and diverse behavior of interfaces is still an active area of research, and to the author's knowledge there are as yet no predictive models for the energy and morphology of interfaces with arbitrary character. The aim of this thesis is to develop a novel model for interface energy and morphology that i) provides accurate results (especially regarding "energy cusp" locations) for interfaces with arbitrary character, ii) depends on a small set of material parameters, and iii) is fast enough to incorporate into large scale simulations.

In the first half of the work, a model for planar, immiscible grain boundary is formulated. By building on the assumption that anisotropic grain boundary energetics are dominated by geometry and crystallography, a construction on lattice density functions (referred to as "covariance") is introduced that provides a geometric measure of the order of an interface. Covariance forms the basis for a fully general model of the energy of a planar interface, and it is demonstrated by comparison with a wide selection of molecular dynamics energy data for FCC and BCC tilt and twist boundaries that the model accurately reproduces the energy landscape using only three material parameters. It is observed that the planar constraint on the model is, in some cases, over-restrictive; this motivates an extension of the model.

In the second half of the work, the theory of faceting in interfaces is developed and applied to the planar interface model for grain boundaries. Building on previous work in mathematics and materials science, an algorithm is formulated that returns the minimal possible energy attainable by relaxation and the corresponding relaxed morphology for a given planar energy model. It is shown that the relaxation significantly improves the energy results of the planar covariance model for FCC and BCC tilt and twist boundaries. The ability of the model to accurately predict faceting patterns is demonstrated by comparison to molecular dynamics energy data and experimental morphological observation for asymmetric tilt grain boundaries. It is also demonstrated that by varying the temperature in the planar covariance model, it is possible to reproduce a priori the experimentally observed effects of temperature on facet formation.

Finally, the range and scope of the covariance and relaxation models, having been demonstrated by means of extensive MD and experimental comparison, future applications and implementations of the model are explored.

Spectroscopic investigations of inter- and intramolecular processes in crystalline benzene

I. Introductory Remarks

A brief discussion of the overall organization of the thesis is presented along with a discussion of the relationship between this thesis and previous work on the spectroscopic properties of benzene.

II. Radiationless Transitions and Line broadening

Radiationless rates have been calculated for the ³B_1u→¹A_1g transitions of benzene and perdeuterobenzene as well as for the ¹B_2u→¹A_1g transition of benzene. The rates were calculated using a model that considers the radiationless transition as a tunneling process between two multi-demensional potential surfaces and assuming both harmonic and anharmonic vibrational potentials. Whenever possible experimental parameters were used in the calculation. To this end we have obtained experimental values for the anharmonicities of the carbon-carbon and carbon-hydrogen vibrations and the size of the lowest triplet state of benzene. The use of the breakdown of the Born-Oppenheimer approximation in describing radiationless transitions is critically examined and it is concluded that Herzberg-Teller vibronic coupling is 100 times more efficient at inducing radiationless transitions.

The results of the radiationless transition rate calculation are used to calculate line broadening in several of the excited electronic states of benzene. The calculated line broadening in all cases is in qualitative agreement with experimental line widths.

III. ³B_1u←¹A_1g Absorption Spectra

The ³B_1u←¹A_1g absorption spectra of C₆H₆ and C₆D₆ at 4.2˚K have been obtained at high resolution using the phosphorescence photoexcitation method. The spectrum exhibits very clear evidence of a pseudo-Jahn-Teller distortion of the normally hexagonal benzene molecule upon excitation to the triplet state. Factor group splitting of the 0 – 0 and 0 – 0 + v exciton bands have also been observed. The position of the mean of the 0 – 0 exciton band of C₆H₆ when compared to the phosphorescence origin of a C₆H₆ guest in a C₆D₆ host crystal indicates that the “static” intermolecular interactions between guest and hose are different for C₆H₆ and C₆D₆. Further investigation of this difference using the currently accepted theory of isotopic mixed crystals indicates that there is a 2cm^-1 shift of the ideal mixed crystal level per hot deuterium atom. This shift is observed for both the singlet and triplet states of benzene.

IV. ³E_1u←¹A_1g, Absorption Spectra

The ³E_1u←¹A_1g absorption spectra of C₆H₆ and C₆D₆ at 4.2˚K have been obtained using the phosphorescence photoexcitation technique. In both cases the spectrum is broad and structureless as would be expected from the line broadening calculations.