Well-defined randomly functionalized polyolefins produced by catalysis form an interesting class of polymers with great potential for various applications. One of the major challenges for the production of these materials forms the incompatibility of the commonly used electrophilic group 4 metal based catalysts and the desired nucleophilic, especially protic functionalities like hydroxyl and carboxylic acid groups. Although pacification of the protic functionality remains necessary, it was found that lowering the oxidation state of a constrained geometry type of catalyst from Ti­(IV) to Ti­(III) turned the catalyst unexpectedly tolerant to a wide variety of aluminum alkyl pacified, hydroxyl-functionalized olefin comonomers. The catalyst’s tendency to undergo chain transfer to aluminum, which was found to be intensified by the presence of aluminum alkyl pacified, hydroxyl-functionalized comonomers, can be efficiently suppressed by the addition of a sterically hindered phenol such as 2,6-bis­(1,1-dimethylethyl)-4-methylphenol (BHT). Surprisingly, the addition of BHT also increases the catalyst’s affinity to incorporate these functionalized comonomers.

Based on conceptual density functional theory, two new descriptors, the normalized atom-condensed Fukui functions (NFFs) and bond deformation kernel (BDK), are proposed to describe the O-H stretching frequency shifts in water halide-ion clusters by including local polarizations in the system. NFF, along with BDK, can be successfully used to describe interactions between different atoms, especially in cases where polarizations are quite important.

The behavior of local reactivity descriptors such as condensed fukui functions, “relative electrophilicity”, and “relative nucleophilicity” was studied as the complexation reaction of BH3 or fluoroboranes and NH3 proceeds. This study reveals the change of these descriptors of different atoms during the reaction. The case study indicates the general properties of descriptors in a reactive surface.

We present a theoretical study of the ionization potential in small anionic gold clusters, using density functional theory, with and without exact-exchange, and many body perturbation theory, namely the G0W0 approach. We find that G0W0 is the best approach and correctly describes the first ionization potential with an accuracy of about 0.1 eV. PACS numbers: 31.15.xm,,33.15.Ry