Stereomutations in silicate oligomerization: the role of steric hindrance and intramolecular hydrogen bonding.

Stereomutation has previously been explored in the literature with regard to the different mechanisms and activation energy barriers between different forms. However, the forces which govern stereomutations within the intermediate steps in chemical reactions have not been explored previously, a topic addressed in this article. The process of silicate oligomerization has been chosen in this study and it is demonstrated that steric hindrance of molecules and intramolecular hydrogen bonding govern the stereomutation of intermediate pentacoordinate silicon compounds in the silicate oligomerization process. It could be observed that the combined effect of intramolecular hydrogen bonding and steric hindrance in the silicate oligomerization process facilitates the conventional berry pseudorotation mechanism rather than other pseudorotation mechanisms reported in the literature.

Noncovalent Interactions in Mechanical Response of Thermoset Epoxy Resin.

Free volume in polymers is known to influence the mechanical response of the polymers. Noncovalent interactions such as hydrogen bonds, Coulombic electrostatic interactions, and van der Waals interactions are present within these free volume regions. The manuscript presents a comprehensive identification, characterization, and evolution of noncovalent interactions as a thermoset epoxy resin (typically used as an interfacial adhesive material) is subjected to uniaxial tension, shear, and shock loading. Even though noncovalent interactions dominate uniaxial tension and shear response (up to strain levels of 50% wherein covalent bond dissociation is not observed), both covalent and noncovalent interactions define response for shock loading. Van der Waals interactions dominate the response as the samples are subjected to strain levels of 50% in tension and shear. In contrast, hydrogen bonds influence shock response.

Catalytic Behavior of Hydrogen Bonded Water in Oligomerization of Silicates.

Even though much research has been done to demonstrate the oligomerization of zeolites and silicates, there has been almost no study that investigates the role of hydrogen bonds in these reaction pathways. This study demonstrates the catalytic activity of hydrogen bonds in the silicate oligomerization reaction pathway. The presence of hydrogen bonding has been shown to enhance the energetic favorability of the anionic-I mechanism. Catalysis is prevalent in the Si-OH rupture process of the reaction pathway. Simultaneously, the dependence of the activation barrier on the equatorial or apical nature of the cleaving hydroxyl group has also been shown. The preceding steps such as condensation and fluxional influence the strength of hydrogen bonds. An increase in hydrogen bond strength enhances its catalytic effect, leading to a higher extent of reduction in the activation barrier of the particular reaction step. Even though the quantum study focuses on the oligomerization of calcium silicate as a test case, it can be anticipated that such similar effects can be perceived in general for the oligomerization of silicates containing metallic ions in sol-gel chemistry and zeolite synthesis.

Silica dimerization in the presence of divalent cations.

The presence of monovalent cations and organic tetraalkylammonium ions is known to affect the reaction pathway and chemical kinetics of the silica oligomerization reaction which is important for sol-gel chemistry studies. A detailed theoretical study focusing on the chemical reaction pathway for the dimerisation process in the presence of a divalent cation is presented in this study. Different condensation pathways such as neutral, anionic-I and anionic-II along with their relative possibilities in dimerization have been explored. It has been demonstrated that with an increase in the pH of solution, manifested through the presence of deprotonated ions (as in the anionic cases with or without the presence of divalent cations), the activation activation barrier of the dimerization reaction is lowered. It has also been demonstrated that the addition of divalent cations raises the activation barriers for the reaction and delays the overall dimerisation reaction. The stability and bond characteristics of the bridging Si-OH bond of the resulting dimer products have also been determined. Activation energy barriers for the anionic case have also been observed to vary based upon the dihedral arrangement of the hydroxyl group bonded with the silicon and the orientation of the nucleophilic attack.

Intermolecular Dynamics of Water: Suitability of Reactive Interatomic Potential.

Reactive interatomic potentials for water have been developed by researchers based on their ability of bond breaking and formation, which have numerous advantages and applications in different fields. The question that is being addressed in this work is whether these reactive interatomic potentials properly account for the intermolecular dynamics of water that includes both hydrogen bonding as well as librational motions. It should be noted that breaking and reformation of hydrogen bonds occur prior to covalent bond breaking of water molecules (which requires a significant amount of energy), which has numerous applications in absorption as well as solvation problems. Based on correlations with experimental observations, it has been demonstrated that the current forms of the reactive potentials perform poorly in comparison to other well-established empirical interatomic potential models of water, such as TIP4P/2005f, with regard to the intermolecular dynamics of water. Translational and rotational diffusivities, power spectra, and hydrogen-bond lifetime analyses are carried out and compared to available experimental data as well as those obtained from TIP4P/2005f models to arrive at such conclusions.

Intermolecular dynamics of ultraconfined interlayer water in tobermorite: influence on mechanical performance.

Ultraconfined interlayer water within the tobermorite molecular structure is responsible for changes in the uniaxial tensile and compressive response of the family of tobermorites: 9, 11 and 14 Å. These confined interlayer water molecules are engaged in solvation of cations and anions within the tobermorite structure, which has been demonstrated through the intermolecular vibrational spectra and hydrogen bond lifetime of the water molecules. This study demonstrates that instead of ionization of water molecules (as proposed in an earlier study), breaking of hydrogen bonds of water is more plausible leading to solvation of ions within the molecular structure of tobermorite. A schematic of the coordinate covalent bonds between the water molecules and the cations and anions of the tobermorite structure has been proposed in this study.