Investigation of Frustrated Quasi-One-Dimensional Quantum Spin-Chain Materials

Copper arsenite CuAs2O4 and Copper antimonite CuSb2O4 are S=1/2 (Cu2+ 3d9 electronic configuration) quasi-one-dimensional quantum spin-chain compounds. Both compounds crystallize with tetragonal structures containing edge sharing CuO6 octahedra chains which experience Jahn-Teller distortions. The basal planes of the octahedra link together to form CuO2 ribbon-chains which harbor Cu2+ spin-chains. These compounds are magnetically frustrated with competing nearest-neighbour and next-nearest-neighbour intrachain spin-exchange interactions. Despite the similarities between CuAs2O4 and CuSb2O4, they exhibit very different magnetic properties. In this thesis work, the physical properties of CuAs2O4 and CuSb2O4 are investigated using a variety of experimental techniques which include x-ray diffraction, magnetic susceptibility measurements, heat capacity measurements, Raman spectroscopy, electron paramagnetic resonance, neutron diffraction, and dielectric capacitance measurements. CuAs2O4 exhibits dominant ferromagnetic nearest-neighbour and weaker antiferromagnetic next-nearest-neighbour intrachain spin-exchange interactions. The ratio of the intrachain interactions amounts to Jnn/Jnnn = -4.1. CuAs2O4 was found to order with a ferromagnetic groundstate below TC = 7.4 K. An extensive physical characterization of the magnetic and structural properties of CuAs2O4 was carried out. Under the effect of hydrostatic pressure, CuAs2O4 was found to undergo a structural phase transition at 9 GPa to a new spin-chain structure. The structural phase transition is accompanied by a severe alteration of the magnetic properties. The high-pressure phase exhibits dominant ferromagnetic next-nearest-neighbour spin-exchange interactions and weaker ferromagnetic nearest-neighbour interactions. The ratio of the intrachain interactions in the high-pressure phase was found to be Jnn/Jnnn = 0.3. Structural and magnetic characterizations under hydrostatic pressure are reported and a relationship between the structural and magnetic properties was established. CuSb2O4 orders antiferromagnetically below TN = 1.8 K with an incommensurate helicoidal magnetic structure. CuSb2O4 is characterized by ferromagnetic nearest-neighbour and antiferromagnetic next-nearest-neighbour spin-exchange interactions with Jnn/Jnnn = -1.8. A (H, T) magnetic phase diagram was constructed using low-temperature magnetization and heat capacity measurements. The resulting phase diagram contains multiple phases as a consequence of the strong intrachain magnetic frustration. Indications of ferroelectricity were observed in the incommensurate antiferromagnetic phase.

DFT Studies of the Organocatalytic Aldol Reaction and a Frustrated Lewis Pair

The computational study, and in particular the density functional theory (DFT) study of the organocatalytic α-chlorination-aldol reaction and the chiral backbone Frustrated Lewis Pair (FLP) system served as a valuable tool for experimental purposes. This thesis describes methods to consider different transition states of the proline- catalyzed α-chlorination aldol reaction to determine the reasonable transition state in the reaction between the enamine and α-chloro aldehydes. Moreover, the novel intramolecular Frustrated Lewis pair based on a chiral backbone for the asymmetric hydrogenation of imines and enamines was designed and the ability of hydrogen splitting by this new FLP system was examined by computational modeling and calculating the hydrogen activation energy barrier.

The Effects of Magnetic Dilution and Applied Pressure on Several Frustrated Spinels

The effects of magnetic dilution and applied pressure on frustrated spinels GeNi2O4, GeCo2O4, and NiAl2O4 are reported. Dilution was achieved by substitution of Mg2+ in place of magnetically active Co2+ and Ni2+ ions. Large values of the percolation thresholds were found in GeNi(2-x)MgxO4. Specifically, pc1 = 0.74 and pc2 = 0.65 in the sub-networks associated with the triangular and kagome planes, respectively. This anomalous behaviour may be explained by the kagome and triangular planes behaving as coupled networks, also know as a network of networks. In simulations of coupled lattices that form a network of networks, similar anomalous percolation threshold values have been found. In addition, at dilution levels above x=0.30, there is a T^2 dependency in the magnetic heat capacity which may indicate two dimensional spin glass behaviour. Applied pressures in the range of 0 GPa to 1.2 GPa yield a slight decrease in ordering temperature for both the kagome and triangular planes. In GeCo(2-x)MgxO4, the long range magnetic order is more robust with a percolation threshold of pc=0.448. Similar to diluted nickel germanate, at low temperatures, a T^2 magnetic heat capacity contribution is present which indicates a shift from a 3D ordered state to a 2D spin glass state in the presence of increased dilution. Dynamic magnetic susceptibility data indicate a change from canonical spin glass to a cluster glass behaviour. In addition, there is a non-linear increase in ordering temperature with applied pressure in the range P = 0 to 1.0 GPa. A spin glass ground state was observed in Ni(1-x)MgxAl2O4 for (x=0 to 0.375). Analysis of dynamic magnetic susceptibility data yield a characteristic time of tau* = 1.0x10^(-13) s, which is indicative of canonical spin glass behaviour. This is further corroborated by the linear behaviour of the magnetic specific heat contribution. However, the increasing frequency dependence of the freezing temperature suggests a trend towards spin cluster glass formation.

Monte Carlo study of the XY-model on quasi-periodic lattices

Monte Carlo Simulations were carried out using a nearest neighbour ferromagnetic XYmodel, on both 2-D and 3-D quasi-periodic lattices. In the case of 2-D, both the unfrustrated and frustrated XV-model were studied. For the unfrustrated 2-D XV-model, we have examined the magnetization, specific heat, linear susceptibility, helicity modulus and the derivative of the helicity modulus with respect to inverse temperature. The behaviour of all these quatities point to a Kosterlitz-Thouless transition occuring in temperature range Te == (1.0 -1.05) JlkB and with critical exponents that are consistent with previous results (obtained for crystalline lattices) . However, in the frustrated case, analysis of the spin glass susceptibility and EdwardsAnderson order parameter, in addition to the magnetization, specific heat and linear susceptibility, support a spin glass transition. In the case where the 'thin' rhombus is fully frustrated, a freezing transition occurs at Tf == 0.137 JlkB , which contradicts previous work suggesting the critical dimension of spin glasses to be de > 2 . In the 3-D systems, examination of the magnetization, specific heat and linear susceptibility reveal a conventional second order phase transition. Through a cumulant analysis and finite size scaling, a critical temperature of Te == (2.292 ± 0.003) JI kB and critical exponents of 0:' == 0.03 ± 0.03, f3 == 0.30 ± 0.01 and I == 1.31 ± 0.02 have been obtained.

The effects of language complexity in a counterattitudinal appeal to laypeople : an application of the elaboration likelihood model of persuasion to a legal issue

The effects of a complexly worded counterattitudinal appeal on laypeople's attitudes toward a legal issue were examined, using the Elaboration Likelihood Model (ELM) of persuasion as a theoretical framework. This model states that persuasion can result from the elaboration and scrutiny of the message arguments (i.e., central route processing), or can result from less cognitively effortful strategies, such as relying on source characteristics as a cue to message validity (i.e., peripheral route processing). One hundred and sixty-seven undergraduates (85 men and 81 women) listened to eitller a low status or high status source deliver a counterattitudinal speech on a legal issue. The speech was designed to contain strong or weak arguments. These arguments were 'worded in a simple and, therefore, easy to comprehend manner, or in a complex and, therefore, difficult to comprehend manner. Thus, there were three experimental manipulations: argument comprehensibility (easy to comprehend vs. difficult to comprehend), argumel11 strength (weak vs. strong), and source status (low vs. high). After listening to tIle speec.J] participants completed a measure 'of their attitude toward the legal issue, a thought listil1g task, an argument recall task,manipulation checks, measures of motivation to process the message, and measures of mood. As a result of the failure of the argument strength manipulation, only the effects of the comprehel1sibility and source status manipulations were tested. There was, however, some evidence of more central route processing in the easy comprehension condition than in the difficult comprehension condition, as predicted. Significant correlations were found between attitude and favourable and unfavourable thoughts about the legal issue with easy to comprehend arguments; whereas, there was a correlation only between attitude and favourable thoughts 11 toward the issue with difficult to comprehend arguments, suggesting, perhaps, that central route processing, \vhich involves argument scrutiny and elaboration, occurred under conditions of easy comprehension to a greater extent than under conditions of difficult comprehension. The results also revealed, among other findings, several significant effects of gender. Men had more favourable attitudes toward the legal issue than did women, men recalled more arguments from the speech than did women, men were less frustrated while listening to the speech than were ,vomen, and men put more effort into thinking about the message arguments than did women. When the arguments were difficult to comprehend, men had more favourable thoughts and fewer unfavourable thoughts about the legal issue than did women. Men and women may have had different affective responses to the issue of plea bargaining (with women responding more negatively than men), especially in light of a local and controversial plea bargain that occurred around the time of this study. Such pre-existing gender differences may have led to tIle lower frustration, the greater effort, the greater recall, and more positive attitudes for men than for WOlnen. Results· from this study suggest that current cognitive models of persuasion may not be very applicable to controversial issues which elicit strong emotional responses. Finally, these data indicate that affective responses, the controversial and emotional nature ofthe issue, gender and other individual differences are important considerations when experts are attempting to persuade laypeople toward a counterattitudinal position.

Improving Performance of Open Access Clinics

Open Access Scheduling has shown great promise in allowing health care practices to provide same-day access, and to match patients with their regular physicians. However, similarly to traditional clinics where appointments are pre-booked, open access clinics are also frustrated with long waits, long idle time and long overtime due to uncertainties such as patient no-shows, variable service time and variable daily demand. These aspects have not been studied previously in an open access setting. This study investigates different management options to improve clinical performance in terms of patient waiting time, doctor idle time and clinic overtime. Other factors studied with a simulation model include client load and placement of pre-booked slots. Results show that a proper panel size is critical to obtain good performance for open access clinics, and that good choices for management options depend on the client load.