scholarly journals Elucidation of Aqueous Solvent-Mediated Hydrogen-Transfer Reactions by ab Initio Molecular Dynamics and Nudged Elastic-Band Studies of NaBH4 Hydrolysis

2014 ◽  
Vol 118 (37) ◽  
pp. 21385-21399 ◽  
Author(s):  
Ping Li ◽  
Graeme Henkelman ◽  
John A. Keith ◽  
J. Karl Johnson
Keyword(s):  
Molecular Dynamics ◽  
Ab Initio ◽  
Hydrogen Transfer ◽  
Transfer Reactions ◽  
Ab Initio Molecular Dynamics ◽  
Elastic Band ◽  
Aqueous Solvent ◽  
Hydrogen Transfer Reactions

scholarly journals Ab initio molecular dynamics of solvation effects on reactivity at electrified interfaces

2016 ◽  
Vol 113 (34) ◽  
pp. E4937-E4945 ◽  
Author(s):  
Jeffrey A. Herron ◽  
Yoshitada Morikawa ◽  
Manos Mavrikakis
Keyword(s):  
Molecular Dynamics ◽  
Ab Initio ◽  
Density Functional ◽  
Bond Activation ◽  
Methanol Electrooxidation ◽  
Binding Energies ◽  
Ab Initio Molecular Dynamics ◽  
Generalized Gradient ◽  
Elastic Band ◽  
Calculated Activation Energy

Using ab initio molecular dynamics as implemented in periodic, self-consistent (generalized gradient approximation Perdew–Burke–Ernzerhof) density functional theory, we investigated the mechanism of methanol electrooxidation on Pt(111). We investigated the role of water solvation and electrode potential on the energetics of the first proton transfer step, methanol electrooxidation to methoxy (CH3O) or hydroxymethyl (CH2OH). The results show that solvation weakens the adsorption of methoxy to uncharged Pt(111), whereas the binding energies of methanol and hydroxymethyl are not significantly affected. The free energies of activation for breaking the C−H and O−H bonds in methanol were calculated through a Blue Moon Ensemble using constrained ab initio molecular dynamics. Calculated barriers for these elementary steps on unsolvated, uncharged Pt(111) are similar to results for climbing-image nudged elastic band calculations from the literature. Water solvation reduces the barriers for both C−H and O−H bond activation steps with respect to their vapor-phase values, although the effect is more pronounced for C−H bond activation, due to less disruption of the hydrogen bond network. The calculated activation energy barriers show that breaking the C−H bond of methanol is more facile than the O−H bond on solvated negatively biased or uncharged Pt(111). However, with positive bias, O−H bond activation is enhanced, becoming slightly more facile than C−H bond activation.

Assessing the performance of ab initio classical valence bond methods for hydrogen transfer reactions

2017 ◽  
Vol 1116 ◽  
pp. 234-241 ◽  
Author(s):  
Itay Karach ◽  
Alina Botvinik ◽  
Donald G. Truhlar ◽  
Wei Wu ◽  
Avital Shurki
Keyword(s):  
Ab Initio ◽  
Hydrogen Transfer ◽  
Valence Bond ◽  
Transfer Reactions ◽  
Hydrogen Transfer Reactions

Combustion Driven by Fragment-based Ab Initio Molecular Dynamics Simulation

2019 ◽  
Author(s):  
Liqun Cao ◽  
Jinzhe Zeng ◽  
Mingyuan Xu ◽  
Chih-Hao Chin ◽  
Tong Zhu ◽  
...  
Keyword(s):  
Molecular Dynamics ◽  
Ab Initio ◽  
Large Scale ◽  
Methane Combustion ◽  
Combustion Method ◽  
Dynamics Simulation ◽  
Ab Initio Molecular Dynamics ◽  
Computational Time ◽  
Combustion Mechanism ◽  
Daily Lives

Combustion is a kind of important reaction that affects people's daily lives and the development of aerospace. Exploring the reaction mechanism contributes to the understanding of combustion and the more efficient use of fuels. Ab initio quantum mechanical (QM) calculation is precise but limited by its computational time for large-scale systems. In order to carry out reactive molecular dynamics (MD) simulation for combustion accurately and quickly, we develop the MFCC-combustion method in this study, which calculates the interaction between atoms using QM method at the level of MN15/6-31G(d). Each molecule in systems is treated as a fragment, and when the distance between any two atoms in different molecules is greater than 3.5 Å, a new fragment involved two molecules is produced in order to consider the two-body interaction. The deviations of MFCC-combustion from full system calculations are within a few kcal/mol, and the result clearly shows that the calculated energies of the different systems using MFCC-combustion are close to converging after the distance thresholds are larger than 3.5 Å for the two-body QM interactions. The methane combustion was studied with the MFCC-combustion method to explore the combustion mechanism of the methane-oxygen system.

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