RHF, MP2 and DFT calculations were carried out for the unhydrated and explicitly solvated (by five water molecules) putative zwitterionic complexes formed in the aminolysis of oxo {(O, O)} and thio {(O, S), (S, O) and (S, S)} carbonates [MeO−C(=Y)−Y Ar] and carbamates [NH 2 −C(=Y)−Y Ar, where Y and Y are O or S] with ammonia. The reorganization energy of the carbonyl carbon from an sp 2 to an sp 3 center, i.e., the energy needed to form a zwitterionic tetrahedral intermediate, was inversely related to the experimental rate of the aminolysis of carbonates as Y and Y are varied, (O, S) < (O, O) < (S, S) < (S, O). For carbamates the reorganization energy is the highest and the solvation energy is the lowest among ester, carbonate and carbamate series, which is suggestive of the difficulty of zwitterionic intermediate formation and changeover to a concerted mechanism found experimentally for the aminolysis of the carbamates.

As an organic/inorganic hybrid possessing advantages from the combination of their own unique properties, conducting polyaniline (PANI)-titanium dioxide ( TiO 2) hybrid particles were synthesized by an oxidation polymerization of aniline, and their ER characteristics were examined. Our aim was to study the ER behavior of highly potential ER-active particles using conducting polymer and TiO 2 nanoparticle with relatively high dielectric constant. In addition, we also investigated its ER behavior as a function of particle fraction of TiO 2 under an applied electric field. The result was interpreted in terms of the dielectric relaxation mismatch. The fast relaxation time of PANI/TiO 2 hybrid was considered to enhance electrostatic force over shear force under a hydrodynamic flow, showing its improved ER performance.

ChemInform Abstract Calculations on the gas-phase reaction of the ethylenes (I) with bare or monosolvated methoxide ion are carried out by the AM1 method. In all reactions the methoxide approaches in plane but in addition reactions subsequently rotates out of plane to form tetrahedral complexes. All reactions of bare methoxide, mainly the β-addition, are exothermic. In the case of the β-addition the excess energy is carried by the adduct and renders it unstable. The α-H+ abstraction by a monosolvated methoxide is endothermic for (Ia).

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The gas‐phase thermal decomposition reactions of esters (I) are studied theoretically by MNDO and AM1.