An understanding of chemoselective hydrogenation on crotonaldehyde over Pt(111) in the free energy landscape: The microkinetics study based on first-principles calculations

Microkinetic model is developed in the free energy landscape based on density functional theory (DFT) to quantitatively investigate the reaction mechanism of chemoselective partial hydrogenation of crotonaldehyde to crotyl alcohol over Pt(1 1 1) at the temperature of 353 K. Three different methods (mobile, immobile and collision theory models) were carried out to obtain free energy barrier of adsorption/desorption processes. The results from mobile and collision theory models are similar. The calculated TOFs from both models are close to the experiment value. However, for the immobile model, in which the free energy barrier of desorption approaches the energy barrier, the calculated TOF is 2 orders of magnitude lower than the other models. The difficulty of adsorption/ desorption may be overestimated in the immobile model. In addition, detailed analyses show that for the surface hydrogenation elementary steps, the entropy and internal energy effects are small under the reaction condition, while the zero-point-energy (ZPE) correction is significant, especially for the multi-step hydrogenation reaction. The total energy with the ZPE correction approaches to the full free energy calculation for the surface reaction under the reaction condition. (c) 2011 Elsevier B.V. All rights reserved.

Folklore’s Timeless Past, Ireland’s Present Past, and the Perception of Rural Houses in Early Historic Ireland

This study examines how the archaeology of historic Ireland has been interpreted. Two approaches to the history and archaeology of Ireland are identified. The first, the timeless past, has its roots in a neo-Lamarckian view of the past. This perspective was particularly developed in the work of geographer and ethnographer, Estyn Evans. The second view, associated in particular with a nationalist approach to Ireland’s past, looked to the west of the country where it was believed the culture had been preserved largely unchanged and in its purest form. The continuing impact of these frameworks upon the interpretation of rural settlement in the period 1200– 1700 is examined. It is argued that historians and archaeologists alike have underestimated the quality of buildings.

Dissociations between motor timing, motor coordination, and time perception after the administration of alcohol or caffeine

The impacts of psychoactive drugs on timing have usefully informed theories of timing and its substrates.

Trauma typology as a risk factor for aggression and self-harm in a complex PTSD population: The mediating role of alterations in self-perception

This study examined the role of prolonged, repeated traumatic experiences such as childhood and sectarian trauma in the development of posttraumatic aggression and self-harm. Forty-four adult participants attending therapy for complex trauma in Northern Ireland were obtained via convenience sampling. When social desirability was controlled, childhood emotional and physical neglect were significant correlates of posttraumatic hostility and history of self-harm. These relationships were mediated by alterations in self-perception (e.g., shame, guilt). Severity of sectarian-related experiences was not related to self-destructive behaviors. Moreover, none of the trauma factors were related to overt aggressive behavior. The findings have implications for understanding risk factors for posttraumatic aggression and self-harm, as well as their treatment. © 2013 Copyright Taylor & Francis Group, LLC.