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.

Revision over Partial Pre-orders: A Postulational Study

Belief revision is the process that incorporates, in a consistent way,
a new piece of information, called input, into a belief base. When both belief
bases and inputs are propositional formulas, a set of natural and rational properties, known as AGM postulates, have been proposed to define genuine revision operations. This paper addresses the following important issue : How to revise a partially pre-ordered information (representing initial beliefs) with a new partially pre-ordered information (representing inputs) while preserving AGM postulates? We first provide a particular representation of partial pre-orders (called units) using the concept of closed sets of units. Then we restate AGM postulates in this framework by defining counterparts of the notions of logical entailment and logical consistency. In the second part of the paper, we provide some examples of revision operations that respect our set of postulates. We also prove that our revision methods extend well-known lexicographic revision and natural revision for both cases where the input is either a single propositional formula or a total pre-order.