High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Effect of water on olivine single crystals plasticity, deformed under high pressure and high temperature

The Earth's upper mantle, mainly composed of olivine, is seismically anisotropic. Seismic anisotropy attenuation has been observed at 220km depth. Karato et al. (1992) attributed this attenuation to a transition between two deformation mechanisms, from dislocation creep above 220km to diffusion creep below 220km, induced by a change in water content. Couvy (2005) and Mainprice et al. (2005) predicted a change in Lattice Preferred Orientation induced by pressure, which comes from a change of slip system, from [100] slip to [001] slip, and is responsible for the seismic anisotropy attenuation. Raterron et al. (2007) ran single crystal deformation experiments under anhydrous conditions and observed that the slip system transition occurs around 8GPa, which corresponds to a depth of 260Km. Experiments were done to quantify the effects of water on olivine single crystals deformed using D-DIA press and synchrotron beam. Deformations were carried out in uniaxial compression along [110]c, [011]c, and [101]c, crystallographic directions, at pressure ranging from 4 to 8GPa and temperature between 1373 and 1473K. Talc sleeves about the annulus of the single crystals were used as source of water in the assembly. Stress and specimen strain rates were calculated by in-situ X-ray diffraction and time resolved imaging, respectively. By direct comparison of single crystals strain rates, we observed that [110]c deforms faster than [011]c below 5GPa. However above 6GPa [011]c deforms faster than [110]c. This revealed that [100](010) is the dominant slip system below 5GPa, and above 6GPa [001](010) becomes dominant. According to our results, the slip system transition, which is induced by pressure, occurs at 6GPa. Water influences the pressure where the switch over occurs, by lowering the transition pressure. The pressure effect on the slip systems activity has been quantified and the hydrolytic weakening has also been estimated for both orientations. Data also shows that temperature affects the slip system activity. The regional variation of the depth for the seismic anisotropy attenuation, which would depend on local hydroxyl content and temperature variations and explains the seismic anisotropy attenuation occurring at about 220Km depth in the mantle, where the pressure is about 6GPa. Deformation of MgO single crystal oriented [100], [110] and [111] were also performed. The results predict a change in the slip system activity at 23GPa, again induced by pressure. This explains the seismic anisotropy observed in the lower mantle.

The Chef In Society: Origins And Development

In his discourse - The Chef In Society: Origins And Development - Marcel R. Escoffier, Graduate Student, School of Hospitality Management at Florida International University, initially offers: “The role of the modern professional chef has its origins in ancient Greece. The author traces that history and looks at the evolution of the executive chef as a manager and administrator.” “Chefs, as tradespersons, can trace their origins to ancient Greece,” the author offers with citation. “Most were slaves…” he also informs you. Even at that low estate in life, the chef was master of the slaves and servants who were at close hand in the environment in which they worked. “In Athens, a cook was the master of all the household slaves…” says Escoffier. As Athenian influence wanes and Roman civilization picks-up the torch, chefs maintain and increase their status as important tradesmen in society. “Here the first professional societies of cooks were formed, almost a hierarchy,” Escoffier again cites the information. “It was in Rome that cooks established their first academy: Colleqium Coquorum,” he further reports. Chefs, again, increase their significance during the following Italian Renaissance as the scope of their influence widens. “…it is an historical fact that the marriage of Henry IV and Catherine de Medici introduced France to the culinary wonders of the Italian Renaissance,” Escoffier enlightens you. “Certainly the professional chef in France became more sophisticated and more highly regarded by society after the introduction of the Italian cooking concepts.” The author wants you to know that by this time cookbooks are already making important inroads and contributing to the history of cooking above and beyond their obvious informational status. Outside of the apparent European influences in cooking, Escoffier also ephemerally mentions the development of Chinese and Indian chefs. “It is interesting to note that the Chinese, held by at least one theory as the progenitors of most of the culinary heritage, never developed a high esteem for the position of chef,” Escoffier maintains the historical tack. “It was not until the middle 18th Century that the first professional chef went public. Until that time, only the great houses of the nobility could afford to maintain a chef,” Escoffier notes. This private-to-public transition, in conjunction with culinary writing are benchmarks for the profession. Chefs now establish authority and eminence. The remainder of the article devotes itself to the development of the professional chef; especially the melding of two seminal figures in the culinary arts, Cesar Ritz and August Escoffier. The works of Frederick Taylor are also highlighted.

A decision support framework for infrastructure maintenance investment decision-making

Infrastructure management agencies are facing multiple challenges, including aging infrastructure, reduction in capacity of existing infrastructure, and availability of limited funds. Therefore, decision makers are required to think innovatively and develop inventive ways of using available funds. Maintenance investment decisions are generally made based on physical condition only. It is important to understand that spending money on public infrastructure is synonymous with spending money on people themselves. This also requires consideration of decision parameters, in addition to physical condition, such as strategic importance, socioeconomic contribution and infrastructure utilization. Consideration of multiple decision parameters for infrastructure maintenance investments can be beneficial in case of limited funding. Given this motivation, this dissertation presents a prototype decision support framework to evaluate trade-off, among competing infrastructures, that are candidates for infrastructure maintenance, repair and rehabilitation investments. Decision parameters' performances measured through various factors are combined to determine the integrated state of an infrastructure using Multi-Attribute Utility Theory (MAUT). The integrated state, cost and benefit estimates of probable maintenance actions are utilized alongside expert opinion to develop transition probability and reward matrices for each probable maintenance action for a particular candidate infrastructure. These matrices are then used as an input to the Markov Decision Process (MDP) for the finite-stage dynamic programming model to perform project (candidate)-level analysis to determine optimized maintenance strategies based on reward maximization. The outcomes of project (candidate)-level analysis are then utilized to perform network-level analysis taking the portfolio management approach to determine a suitable portfolio under budgetary constraints. The major decision support outcomes of the prototype framework include performance trend curves, decision logic maps, and a network-level maintenance investment plan for the upcoming years. The framework has been implemented with a set of bridges considered as a network with the assistance of the Pima County DOT, AZ. It is expected that the concept of this prototype framework can help infrastructure management agencies better manage their available funds for maintenance.

The correlation of structure and electronic properties near the surface of transition metal oxides

The strong couplings between different degrees of freedom are believed to be responsible for novel and complex phenomena discovered in transition metal oxides (TMOs). The physical complexity is directly responsible for their tunability. Creating surfaces/interfaces add an additional ' man-made' twist, approaching the quantum phenomena of correlated materials. ^ The dissertation focused on the structural and electronic properties in proximity of surface of three prototype TMO compounds by using three complementary techniques: scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and low energy electron diffraction, particularly emphasized the effects of broken symmetry and imperfections like defects on the coupling between charge and lattice degrees of freedom. ^ Ca1.5Sr0.5RuO4 is a layered ruthenate with square lattice and at the boundary of magnetic/orbital instability in Ca2-xSrxRuO4. That the substitution of Sr 2+ with Ca2+ causing RuO6 rotation narrows the dxy band width and changes the Fermi surface topology. Particularly, the γ(dxy) Fermi surface sheet exhibited hole-like in Ca1.5Sr0.5RuO4 in contrast to electron-like in Sr2RuO4, showing a strong charge-lattice coupling. ^ Na0.75CoO2 is a layered cobaltite with triangular lattice exhibiting extraordinary thermoelectric properties. The well-ordered CoO2-terminated surface with random Na distribution was observed. However, lattice constants of the surface are smaller than that in bulk. The surface density of states (DOS) showed strong temperature dependence. Especially, an unusual shift of the minimum DOS occurs below 230 K, clearly indicating a local charging effect on the surface. ^ Cd2Re2O7 is the first known pyrochlore oxide superconductor (Tc ∼ 1K). It exhibited an unusual second-order phase transition occurring at TS1 = 200 K and a controversial first-order transition at TS2 = 120 K. While bulk properties display large anomalies at TS1 but rather subtle and sample-dependent changes at TS2, the surface DOS near the EF show no change at T s1 but a substantial increase below TS2---a complete reversal as the signature for the transitions. We argued that crystal imperfections, mainly defects, which were considerably enhanced at the surface, resulted in the transition at TS2. ^