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Theses

Solvation and adsorptions at the solid / water interface : developments and applications

Abstract : This Ph.D. thesis investigates the impact of solvation on adsorption at the solid/water interfaceand presents method developments to unravel and realistically capture these effectsin theoretical studies.The SolvHybrid package was built to compute the solvation free energy difference betweena molecule solvated in bulk water and adsorbed at the Pt(111)/ water interface. SolvHybridis based on a hybrid QM/MM description and thermodynamic integration. The schemewas validated on experimentally available adsorption free energies of benzene and phenol.To increase the quality of its MM description and widen the applicability of SolvHybridbeyond the Pt(111)/water interface, forcefield developments have been pursued.The pairwise additive GAL19 forcefield was proposed to model water/noble-metal interactions.It demonstrated a great accuracy to reproduce the adsorption energy of a watermolecule on ten metallic (100) or (111) surface made of Cu, Ag, Au, Pd, Pt. This forcefield was later extended to more corrugated surfaces and nano-particles. To understandthe limitations of our pairwise additive force field for water layer structures, we also decomposedthe total interaction energy of water layers on metallic surfaces as computedby DFT. Apart from additive water/metal contributions, polarisation and charge-transferwere determined and quantified as major many-body effects, suggesting routes to secondgeneration forcefields.Metallic oxides were then investigated as a subsequent step in surface complexity, becauseof their tendency to react and even restructure in contact with water. Metadynamics waschosen to investigate the surface reconstruction of alumina in water. Our work demonstratedthe crucial role of the surface water structure in this process and its modificationin the presence of adsorbates. A panoply of methods (SolvHybrid, a GAL19-inspired forcefield,metadynamics, and thermodynamic integration) were then applied and comparedon the complex chemistry of the adsorption of ethanol on alumina in water, combining allprevious challenges.
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Submitted on : Monday, July 12, 2021 - 2:57:13 PM
Last modification on : Tuesday, January 4, 2022 - 5:49:42 AM
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  • HAL Id : tel-03284332, version 1

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Paul Clabaut. Solvation and adsorptions at the solid / water interface : developments and applications. Theoretical and/or physical chemistry. Université de Lyon, 2021. English. ⟨NNT : 2021LYSEN015⟩. ⟨tel-03284332⟩

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