Solvation Free Energies and Adsorption Energies at the Metal/Water Interface from Hybrid Quantum-Mechanical/Molecular Mechanics Simulations

Clabaut, Paul; Schweitzer, Benjamin; Götz, Andreas W.; Michel, Carine; Steinmann, Stephan N.

doi:10.1021/acs.jctc.0c00632

Cited by 49 publications

(76 citation statements)

References 78 publications

(157 reference statements)

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“…The structure and the dynamics of water molecules adsorbed at metallic surfaces is now well understood thanks to the combination of advanced experimental (e.g., surface specific in situ vibrational spectroscopies and synchrotron-based techniques) (5-8) and computational (8)(9)(10)(11)(12)(13)(14)(15)(16) methods. A very interesting result arising from these studies is the existence of hydrophobic effects at the interface due to the peculiar organization of the hydrogen bond (HB) network of the adsorbed water molecules (17).…”

mentioning

confidence: 99%

Size dependence of hydrophobic hydration at electrified gold/water interfaces

Serva

Salanne

Havenith

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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Hydrophobic hydration at metal/water interfaces actively contributes to the energetics of electrochemical reactions, e.g. CO2 and N2 reduction, where small hydrophobic molecules are involved. In this work, constant applied potential molecular dynamics is employed to study hydrophobic hydration at a gold/water interface. We propose an adaptation of the Lum–Chandler–Weeks (LCW) theory to describe the free energy of hydrophobic hydration at the interface as a function of solute size and applied voltage. Based on this model we are able to predict the free energy cost of cavity formation at the interface directly from the free energy cost in the bulk plus an interface-dependent correction term. The interfacial water network contributes significantly to the free energy, yielding a preference for outer-sphere adsorption at the gold surface for ideal hydrophobes. We predict an accumulation of small hydrophobic solutes of sizes comparable to CO or N2, while the free energy cost to hydrate larger hydrophobes, above 2.5-Å radius, is shown to be greater at the interface than in the bulk. Interestingly, the transition from the volume dominated to the surface dominated regimes predicted by the LCW theory in the bulk is also found to take place for hydrophobes at the Au/water interface but occurs at smaller cavity radii. By applying the adapted LCW theory to a simple model addition reaction, we illustrate some implications of our findings for electrochemical reactions.

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mentioning

confidence: 99%

Size dependence of hydrophobic hydration at electrified gold/water interfaces

Serva

Salanne

Havenith

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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“…The MMSolv computations were conducted using the method and workflow described in our previous work for the evaluation of the adsorption free energy of benzene or phenol on a Pt(111) surface. 25 The γ-alumina slab is frozen. Lennard-Jones parameters for γ-alumina atoms are taken from the CLAYFF forcefield.…”

Section: Molecular Mechanics Computations With Ambermentioning

confidence: 99%

“…[20][21][22][23][24] For instance, using our recent MMSolv approach, the adsorption energy at the water/Pt interface of phenol and benzene was predicted semi-quantitatively. 25 This hybrid scheme highlighted the importance of the desolvation of the surface in limiting the adsorption at the interface.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic investigation and free energies of the reactive adsorption of ethanol at the alumina/water interface

Clabaut

Rey

Réocreux

et al. 2021

Preprint

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Controlling the adsorption/desorption of molecules at the solid/water interface is central to a diversity of fields from catalysis to batteries. Preventing the desorption of alcohol at the gamma-Al2O3/water interface is key to increase the stability of this catalyst support to perform reactions in water. Taking ethanol as a typical example, we investigate here the mechanism of desorption of two adsorption modes, namely chemisorbed ethanol and ethoxy, from the interface to the bulk water using three DFT-based simulations. Our 3D well-tempered metadynamics simulations include a bias in solvation, which triggers possible proton transfers with water. They evidence that solvation needs to be increased prior to desorption in both cases. Comparison with static approaches and thermodynamic integration simulations unambiguously identifies ethoxy as the more stable adsorption mode. It is more stable by at least 40 kJ/mol when considering adsorption at the gas/solid interface. And the presence of liquid water yields to a desorption barriers ranging from 89 kJ/mol (thermodynamic integration) to 149 kJ/mol (well-tempered metadynamics). The observed difference between the two biased ab initio molecular dynamics methods can be ascribed to the intrinsic difficulty of sampling the desorbed state vs. the adsorbed state.

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“…When a chemical reaction is clearly targeted as in heterogeneous (electro)-catalysis, computing adsorption energies at the Density Functional Theory (DFT) level is the work-horse, sometimes supplemented with more or less advanced solvent models. [5][6][7] In this field, a great attention is also given to the surface state and its impact. While the surface modification by water for instance can be critical to describe the reactivity in specific cases 8 , it appears that adsorption of small typical fragments follow universal scaling relations on bare surfaces [9][10][11][12] , making the adsorption ranking conserved from one material to the next.…”

Section: Introductionmentioning

confidence: 99%

(Dis)Similarities of adsorption of diverse functional groups over alumina and hematite depending on the surface state

Blanck

Martí

Loehlé

et al. 2021

The Journal of Chemical Physics

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To accelerate the conversion to more sustainable lubricants, there is a need for an improved understanding of the adsorption at the solid/liquid interface. As a first step, the DFT computed adsorption energies can be used to screen the ability of additives to cover a surface. Analogously to what has been found in catalysis with the universal scaling relations, we investigate here if a general universal ranking of additives can be found, independently of the surface considered. We divided our set of 25 diverse representative molecules into aprotic and protic molecules. We compared their adsorption over alumina and hematite, which are models of surface oxidized aluminum and steel, respectively. The adsorption energy ranking of our set is not strongly affected by alumina hydration.In contrast, adsorption on hematite is more strongly affected by hydration since all exposed Fe Lewis acid sites are converted into hydroxylated Brønsted basic sites. However, the ranking obtained on hydrated hematite is close to the one obtained on dry alumina, paving the road to a fast screening of additives. In our library, protic molecules are more strongly adsorbed than non-protic molecules. In particular, methyl and dimethyl phosphates are the most strongly adsorbed ones, followed by Nmethyldiethanolamine, succinimide and ethanoic acid. Additives combining these functional groups are expected to strongly adsorb at the solid/liquid interface and, therefore, likely to be relevant components of lubricant formulations.

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Solvation Free Energies and Adsorption Energies at the Metal/Water Interface from Hybrid Quantum-Mechanical/Molecular Mechanics Simulations

Cited by 49 publications

References 78 publications

Size dependence of hydrophobic hydration at electrified gold/water interfaces

Size dependence of hydrophobic hydration at electrified gold/water interfaces

Mechanistic investigation and free energies of the reactive adsorption of ethanol at the alumina/water interface

(Dis)Similarities of adsorption of diverse functional groups over alumina and hematite depending on the surface state

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