Hydrogen migration in BaTiO3-based dielectrics under high humidity and electric field bias

This study investigates the possibility of hydrogen migration in BaTiO3-based dielectrics to improve the electrical reliability of multi-layer ceramic capacitors under conditions of high temperature, humidity, and electric field bias. It was observed that the deuterium in the dielectric drifted and migrated with the electric field, suggesting that deuterium exists as D+. The activation energy was found to be 0.34 eV, which is lower than that observed in previous studies. This finding offers a better understanding of the mechanism behind the migration of deuterium in a dielectric, which is highly relevant to future research in dielectrics and electronic components.

Homogeneous Gold Catalysis: Mechanistic Investigation of Hydroalkoxylation of Various Alkynes

<p>The reaction mechanism of the gold(III)-catalysed hydroalkoxylation of alkynes is studied to provide a deeper understanding of homogeneous gold catalysis. The study is conducted computationally using Density Functional Theory (DFT), with the PBE0 and BP86 functionals and basis sets of triple-ζ quality (aug-cc-pVTZ and aug-cc-pVTZ-PP for the gold atom). It emphasises the mechanisms undergone by various alkynes when they are activated by gold(III) catalysts towards nucleophilic attack to first form an enol ether and followed by a second nucleophilic attack to form a ketal as the final product. Hydrogen bonding networks formed by the solvent methanols are found to play a crucial role in the mechanism especially in the hydrogen migration steps that follow after the nucleophilic attacks. The first nucleophilic attacks are predicted to have rather low activation energies and hence they are expected to proceed fast while the second additions vary in activation barriers, depending on the steric effects in the substrates. The activation barrier for the last hydrogen migration is highest for all of the three reactions investigated and is expected to be the rate determining step. Investigations of internal alkyne reactions reveal that each elementary step requires a higher activation energy compared to terminal alkynes, which explains the low experimental rate of such reactions. Due to the regioselectivity problem in internal alkyne reactions, this results in a mixture of products which is difficult to isolate due to the similarities in their reaction energies. The study also highlights the calculated thermodynamics and kinetics of the reactions, which can be useful in predicting experimental outcomes. Arrhenius plots of concentration of each intermediate species against time were produced to further help the understanding of these mechanisms, whether or not the reactions go to full completion or stop at the formation of enol ether.</p>

Homogeneous Gold Catalysis: Mechanistic Investigation of Hydroalkoxylation of Various Alkynes

<p>The reaction mechanism of the gold(III)-catalysed hydroalkoxylation of alkynes is studied to provide a deeper understanding of homogeneous gold catalysis. The study is conducted computationally using Density Functional Theory (DFT), with the PBE0 and BP86 functionals and basis sets of triple-ζ quality (aug-cc-pVTZ and aug-cc-pVTZ-PP for the gold atom). It emphasises the mechanisms undergone by various alkynes when they are activated by gold(III) catalysts towards nucleophilic attack to first form an enol ether and followed by a second nucleophilic attack to form a ketal as the final product. Hydrogen bonding networks formed by the solvent methanols are found to play a crucial role in the mechanism especially in the hydrogen migration steps that follow after the nucleophilic attacks. The first nucleophilic attacks are predicted to have rather low activation energies and hence they are expected to proceed fast while the second additions vary in activation barriers, depending on the steric effects in the substrates. The activation barrier for the last hydrogen migration is highest for all of the three reactions investigated and is expected to be the rate determining step. Investigations of internal alkyne reactions reveal that each elementary step requires a higher activation energy compared to terminal alkynes, which explains the low experimental rate of such reactions. Due to the regioselectivity problem in internal alkyne reactions, this results in a mixture of products which is difficult to isolate due to the similarities in their reaction energies. The study also highlights the calculated thermodynamics and kinetics of the reactions, which can be useful in predicting experimental outcomes. Arrhenius plots of concentration of each intermediate species against time were produced to further help the understanding of these mechanisms, whether or not the reactions go to full completion or stop at the formation of enol ether.</p>