DFT Study On Reaction Mechanism of Di-tert-butyl Phenol to Di-tert-butyl Hydroxybenzoic Acid

Experimental studies on the Kolbe-Schmitt reaction and its side reactions have made great progresses, however the relative theoretical studies fall behind. In order to study the mechanism of Kolbe-Schmitt reaction with 2,6-di-tert-butylphenol and 2,4-di-tert-butylphenol as reactants, we carried out theoretical calculation studies at M06-2X/Def2-SVP/SMD level of theory using Gaussian 09 D.01 software package. For the reactant 2,6-di-tert-butylphenol, the main product and side product can convert to each other due to the dynamic equilibrium. However for 2,4-di-tert-butylphenol, the main product is thermodynamically favorable due to its lower Gibbs free energy, while the side product is kinetically favorable due to the lower activation energy barrier. We hope the study can shed light on Kolbe-Schmitt reaction.

Impacts of vacancy-induced polarization and distortion on diffusion in solid electrolyte Li 3 OCl

Lithium-rich oxychloride antiperovskites are promising solid electrolytes for enabling next-generation batteries. Here, we report a comprehensive study varying Li + concentrations in Li 3 OCl using ab initio molecular dynamics simulations. The simulations accurately capture the complex interactions between Li + vacancies ( V Li ′ ), the dominant mobile species in Li 3 OCl . The V Li ′ polarize and distort the host lattice, inducing additional non-vacancy-mediated diffusion mechanisms and correlated diffusion events that reduce the activation energy barrier at concentrations as low as 1.5% V Li ′ . Our analyses of discretized diffusion events in both space and time illustrate the critical interplay between correlated dynamics, polarization and local distortion in promoting ionic conductivity in Li 3 OCl . This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.

Electroreduction of Carbon Dioxide by Heterogenized Cofacial Porphyrins

Great attention has been paid to cofacial porphyrins due to their many unique advantages over their monomeric analogs. However, their synthesis is usually complicated. In this work, a facile impregnation method for preparing heterogenized, cofacially stacked porphyrins is proposed. An anionic porphyrin is introduced as an underlayer for immobilization of cationic cobalt porphyrin via electrostatic force. The metal center of the underlying molecule contributes to the electronic structure of the upper cationic cobalt porphyrin. Screening reveals the anionic iron porphyrin to be the most efficient underlayer molecule, lowering the activation energy barrier of CO2 electroreduction, with an improved turnover frequency by 74% to 8.0 s−1 at − 0.6 V versus RHE.

The Activating Effect of Strong Acid for Pd-Catalyzed Directed C–H Activation by Concerted Metalation-Deprotonation Mechanism

A computational study on the origin of the activating effect for Pd-catalyzed directed C–H activation by the concerted metalation-deprotonation (CMD) mechanism is conducted. DFT calculations indicate that strong acids can make Pd catalysts coordinate with directing groups (DGs) of the substrates more strongly and lower the C–H activation energy barrier. For the CMD mechanism, the electrophilicity of the Pd center and the basicity of the corresponding acid ligand for deprotonating the C–H bond are vital to the overall C–H activation energy barrier. Furthermore, this rule might disclose the role of some additives for C–H activation.

Mechanochemical reactions of GaN-Al2O3 interface at the nanoasperity contact: Roles of crystallographic polarity and ambient humidity

Mechanochemical reactions of the GaN-Al2O3 interface offer a novel principle for scientific and technological merits in the micro-/nano-scale ultra-precision surface machining. In this work, the mechanochemical reactions on Ga- and N-faced GaN surfaces rubbed by the Al2O3 nanoasperity as a function of the environmental humidity were investigated. Experimental results indicate that the N-face exhibits much stronger mechanochemical removal over the relative humidity range of 20%–80% than the Ga-face. Increasing water molecules in environmental conditions significantly promotes the interfacial mechanochemical reactions and hence accelerates the atomic attrition on N-face. The hypothesized mechanism of the selective water-involved mechanochemical removal is associated with the dangling bond configuration, which affects the mechanically-stimulated chemical reactions via altering the activation energy barrier to form the bonding bridge across the sliding interface. These findings can enrich the understanding of the underlying mechanism of mechanochemical reactions at GaN-Al2O3 interface and a broad cognition for regulating the mechanochemical reactions widely existing in scientific and engineering applications.

Interplay between spin crossover and proton migration along short strong hydrogen bonds

A proton migration across a short strong hydrogen bond can be triggered by spin crossover of a remote Fe2+ cation, with the onset of a photoinduced activation energy barrier for proton motion at low temperatures.

RATE-LAW APPLICATION TO SIMULATE LITHIUM-BASED CELL EXPERIMENTAL DATA

A rate-law formulation, based on the concept of the overall activation energy barrier, has been developed [1] to simulate the experimental data of a lithium-based electrochemical cell/battery. This short paper illustrates the application of that formulation to simulate the experimental data acquired from the cell during the discharge period.

Intramolecular Proton Transfer in the Isomerization of Hydroxyacetone: A Detailed Characterization Based on Reaction Force Analysis and the Bond Fragility Spectrum

The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (i) a step-wise mechanism that proceeds through formation of the Z-isomer of their shared enediol intermediate, (ii) a step-wise mechanism that forms the E-isomer of the enediol, and (iii) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol^-1. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.

Intramolecular Proton Transfer in the Isomerization of Hydroxyacetone: A Detailed Characterization Based on Reaction Force Analysis and the Bond Fragility Spectrum

The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (i) a step-wise mechanism that proceeds through formation of the Z-isomer of their shared enediol intermediate, (ii) a step-wise mechanism that forms the E-isomer of the enediol, and (iii) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol^-1. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.