Ensemble Effects on Allylic Oxidation within Explicit Solvation Environments

2021 ◽  
Author(s):  
Hung Minh Le ◽  
Mariano Guagliardo ◽  
Anne E. V. Gorden ◽  
Aurora Clark
Keyword(s):  
Molecular Dynamics ◽  
Density Functional Theory ◽  
Density Functional ◽  
Umbrella Sampling ◽  
Catalytic Cycle ◽  
Allylic Oxidation ◽  
Functional Theory ◽  
Sampling Density ◽  
Ensemble Effects ◽  
Explicit Solvation

Umbrella-sampling density functional theory molecular dynamics (DFT-MD) has been employed to study the full catalytic cycle of the allylic oxidation of cyclohexene using a Cu(II) 7-amino-6-((2-hydroxybenzylidene)amino)quinoxalin-2-ol complex in acetonitrile to...

scholarly journals Ensemble Effects of Explicit Solvation on Allylic Oxidation

2021 ◽  
Author(s):  
Hung Le ◽  
Mariano Guagliardo ◽  
Anne Gorden ◽  
Aurora Clark
Keyword(s):  
Gas Phase ◽  
Energy Barrier ◽  
Density Functional ◽  
Umbrella Sampling ◽  
Catalytic Cycle ◽  
Allylic Oxidation ◽  
Free Energy Barrier ◽  
Functional Theory ◽  
Ensemble Effects ◽  
Explicit Solvation

<div>Umbrella-sampling density functional theory molecular dynamics (DFT-MD) has been employed to study the full catalytic cycle of the allylic oxidation of cyclohexene</div><div>using a Cu(II) (E)-6-amino-7-((2-hydroxybenzylidene)amino)quinoxalin-2-ol complex in acetonitrile, which creates the desired cyclohexenone and H 2 O as products. In comparison to prior study using gas-phase DFT, a significant solvent effect is observed on the rate determining allylic H-atom abstraction step (which has a free energy barrier of 12.1 ± 0.2 kcal/mol). During the cycle, the explicit solvation and ensemble sampling of solvent configurations reveals an important dehydrogenation and re-hydrogenation step of the -NH 2 ligand that is essential to catalyst recovery. This work illustrates the importance of ensemble solvent configurational sampling to reveal the breadth of processes that underpin the full catalytic cycle.</div>

scholarly journals Ensemble Effects of Explicit Solvation on Allylic Oxidation

2021 ◽  
Author(s):  
Hung Le ◽  
Mariano Guagliardo ◽  
Anne Gorden ◽  
Aurora Clark
Keyword(s):  
Gas Phase ◽  
Energy Barrier ◽  
Density Functional ◽  
Umbrella Sampling ◽  
Catalytic Cycle ◽  
Allylic Oxidation ◽  
Free Energy Barrier ◽  
Functional Theory ◽  
Ensemble Effects ◽  
Explicit Solvation

<div>Umbrella-sampling density functional theory molecular dynamics (DFT-MD) has been employed to study the full catalytic cycle of the allylic oxidation of cyclohexene</div><div>using a Cu(II) (E)-6-amino-7-((2-hydroxybenzylidene)amino)quinoxalin-2-ol complex in acetonitrile, which creates the desired cyclohexenone and H 2 O as products. In comparison to prior study using gas-phase DFT, a significant solvent effect is observed on the rate determining allylic H-atom abstraction step (which has a free energy barrier of 12.1 ± 0.2 kcal/mol). During the cycle, the explicit solvation and ensemble sampling of solvent configurations reveals an important dehydrogenation and re-hydrogenation step of the -NH 2 ligand that is essential to catalyst recovery. This work illustrates the importance of ensemble solvent configurational sampling to reveal the breadth of processes that underpin the full catalytic cycle.</div>

scholarly journals Ensemble Effects of Explicit Solvation on Allylic Oxidation

2021 ◽  
Author(s):  
Hung Le ◽  
Mariano Guagliardo ◽  
Anne Gorden ◽  
Aurora Clark
Keyword(s):  
Gas Phase ◽  
Energy Barrier ◽  
Density Functional ◽  
Umbrella Sampling ◽  
Catalytic Cycle ◽  
Allylic Oxidation ◽  
Free Energy Barrier ◽  
Functional Theory ◽  
Ensemble Effects ◽  
Explicit Solvation

Umbrella-sampling density functional theory molecular dynamics (DFT-MD) has been employed to study the full catalytic cycle of the allylic oxidation of cyclohexene using a Cu(II) 7-amino-6-((2-hydroxybenzylidene)amino)quinoxalin-2-ol complex in acetonitrile to create cyclohexenone and H$_2$O as products. In comparison to gas-phase DFT, the solvent effect is observed as the rate determining allylic H-atom abstraction step has a free energy barrier of 12.1 $\pm$ 0.2 kcal/mol in solution. During the cycle, the explicit solvation and ensemble sampling of solvent configurations reveals important dehydrogenation and re-hydrogenation steps of the -NH$_2$ group bound to the Cu-site that are essential to catalyst recovery. This work illustrates the importance of ensemble solvent configurational sampling to reveal the breadth of processes that underpin the full catalytic cycle.<br>

Graphene adlayer growth between nonepitaxial graphene and Ni(111) substrate: a promising theoretical scheme

2020 ◽  
Author(s):  
Lijuan Meng ◽  
Jinlian Lu ◽  
Yujie Bai ◽  
Lili Liu ◽  
Tang Jingyi ◽  
...  
Keyword(s):  
Molecular Dynamics ◽  
Density Functional Theory ◽  
Chemical Vapor Deposition ◽  
Molecular Dynamics Simulations ◽  
Vapor Deposition ◽  
Density Functional ◽  
Chemical Vapor ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Dynamics Simulations

Understanding the fundamentals of chemical vapor deposition bilayer graphene growth is crucial for its synthesis. By employing density functional theory calculations and classical molecular dynamics simulations, we have investigated the...

scholarly journals Ab initio molecular dynamics of hydrogen on tungsten surfaces

2021 ◽  
Author(s):  
Alberto Rodríguez-Fernández ◽  
Laurent Bonnet ◽  
Pascal Larrégaray ◽  
Ricardo Díez Muiño
Keyword(s):  
Molecular Dynamics ◽  
Density Functional Theory ◽  
Ab Initio ◽  
Density Functional ◽  
Ab Initio Molecular Dynamics ◽  
Dissociation Process ◽  
Functional Theory ◽  
Classical Molecular Dynamics ◽  
Hydrogen Molecules

The dissociation process of hydrogen molecules on W(110) was studied using density functional theory and classical molecular dynamics.

Solubility of Sodium in Sodium Chloride: A Density Functional Theory Molecular Dynamics Study

2014 ◽  
Vol 161 (8) ◽  
pp. E3042-E3048 ◽  
Author(s):  
Maoyuan Liu ◽  
Patrick Masset ◽  
Angus Gray-Weale
Keyword(s):  
Molecular Dynamics ◽  
Density Functional Theory ◽  
Sodium Chloride ◽  
Density Functional ◽  
Functional Theory

Diffusion of silver in titanium nitride: Insights from density functional theory and molecular dynamics

2021 ◽  
Vol 556 ◽  
pp. 149738
Author(s):  
Veniero Lenzi ◽  
Albano Cavaleiro ◽  
Filipe Fernandes ◽  
Luís Marques
Keyword(s):  
Molecular Dynamics ◽  
Density Functional Theory ◽  
Titanium Nitride ◽  
Density Functional ◽  
Functional Theory
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