3 resultados para THEORETICAL-ANALYSIS

em Brock University, Canada


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Previously, studies investigating emotional face perception - regardless of whether they involved adults or children - presented participants with static photos of faces in isolation. In the natural world, faces are rarely encountered in isolation. In the few studies that have presented faces in context, the perception of emotional facial expressions is altered when paired with an incongruent context. For both adults and 8- year-old children, reaction times increase and accuracy decreases when facial expressions are presented in an incongruent context depicting a similar emotion (e.g., sad face on a fear body) compared to when presented in a congruent context (e.g., sad face on a sad body; Meeren, van Heijnsbergen, & de Gelder, 2005; Mondloch, 2012). This effect is called a congruency effect and does not exist for dissimilar emotions (e.g., happy and sad; Mondloch, 2012). Two models characterize similarity between emotional expressions differently; the emotional seed model bases similarity on physical features, whereas the dimensional model bases similarity on underlying dimensions of valence an . arousal. Study 1 investigated the emergence of an adult-like pattern of congruency effects in pre-school aged children. Using a child-friendly sorting task, we identified the youngest age at which children could accurately sort isolated facial expressions and body postures and then measured whether an incongruent context disrupted the perception of emotional facial expressions. Six-year-old children showed congruency effects for sad/fear but 4-year-old children did not for sad/happy. This pattern of congruency effects is consistent with both models and indicates that an adult-like pattern exists at the youngest age children can reliably sort emotional expressions in isolation. In Study 2, we compared the two models to determine their predictive abilities. The two models make different predictions about the size of congruency effects for three emotions: sad, anger, and fear. The emotional seed model predicts larger congruency effects when sad is paired with either anger or fear compared to when anger and fear are paired with each other. The dimensional model predicts larger congruency effects when anger and fear are paired together compared to when either is paired with sad. In both a speeded and unspeeded task the results failed to support either model, but the pattern of results indicated fearful bodies have a special effect. Fearful bodies reduced accuracy, increased reaction times more than any other posture, and shifted the pattern of errors. To determine whether the results were specific to bodies, we ran the reverse task to determine if faces could disrupt the perception of body postures. This experiment did not produce congruency effects, meaning faces do not influence the perception of body postures. In the final experiment, participants performed a flanker task to determine whether the effect of fearful bodies was specific to faces or whether fearful bodies would also produce a larger effect in an unrelated task in which faces were absent. Reaction times did not differ across trials, meaning fearful bodies' large effect is specific to situations with faces. Collectively, these studies provide novel insights, both developmentally and theoretically, into how emotional faces are perceived in context.

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High temperature superconductors were discovered in 1986, but despite considerable research efforts, both experimental and theoretical, these materials remain poorly understood. Because their electronic structure is both inhomogeneous and highly correlated, a full understanding will require knowledge of quasiparticle properties both in real space and momentum space. In this thesis, we will present a theoretical analysis of the scanning tunneling microscopy (STM) data in BSCCO. We introduce the Bogoliubov-De Gennes Hamiltonian and solve it numerically on a two-dimensional 20 x 20 lattice under a magnetic field perpendicular to the surface. We consider a vortex at the center of our model. We introduce a Zn impurity in our lattice as a microscopic probe of the physical properties of BSCCO. By direct numerical diagonalization of the lattice BogoliubovDe Gennes Hamiltonian for different positions of the impurity, we can calculate the interaction between the vortex and the impurity in a d-wave superconductor.

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The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.