A DFTB-Based Molecular Dynamics Investigation of an Explicitly Solvated Anatase Nanoparticle

O’Carroll, Dáire; English, Niall J.

doi:10.3390/app12020780

Cited by 6 publications

(2 citation statements)

References 27 publications

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“…For performing our metadynamics MD simulations, we selected the MATSCI parameterization of DFTB, which is extensively employed in materials science and has been also tested specifically for the water–titania interface. ,, Since the subtle balance between water–water and water–surface interactions is key to molecular versus dissociative adsorption, we tested the DFTB(MATSCI) level of theory against DFT(PBE) and DFT(HSE06) by computing the dissociation reaction path for a single water molecule at the TiO 2 (101) surface with the NEB approach, as implemented in CP2K (see Figure ). …”

Section: Resultsmentioning

confidence: 99%

Dynamics of Water Dissociative Adsorption on TiO₂ Anatase (101) at Monolayer Coverage and Below

et al. 2022

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TiO2 anatase is a functional material that is exploited in several technological devices from photovoltaics to energy storage, water splitting, and solar-to-fuel photocatalysis. In this context, numerous theoretical studies addressed the interaction of water with the most stable anatase (101) surface and reported undissociated molecular adsorption. However, recent experiments on such surface facet at low water coverage pointed out the presence of OH groups. Motivated by these findings, we report here a first-principles investigation on the adsorption and dissociation at low (θ = 0.25) and full (θ = 1) coverage of the first water monolayer at the (101) anatase surface at 300 K with metadynamics. Our simulations show barrierless water adsorption, and at the same time, the dynamic nature of titania–water interactions allows for the dissociation of water and the possible formation of a partial hydroxylated surface at room temperature. These results highlight the relevance of dynamic in modeling surface–water interactions and provide new insights into the physicochemical properties of the pristine anatase TiO2(101) surface in an aqueous environment.

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Section: Resultsmentioning

confidence: 99%

Dynamics of Water Dissociative Adsorption on TiO₂ Anatase (101) at Monolayer Coverage and Below

et al. 2022

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“…The ReaxFF , reactive force field was tested in the same fashion. DFTB and the ReaxFF are well-known methods that have already been frequently employed in heterogeneous catalysis. − On the other hand, the recently developed GFN methods were first benchmarked against high-level DFT, wave function theory (WFT), and experimental data mainly for organic and metal–organic compounds. ,− However, their promising applications reported in the past few years − together with their low computational cost and their atom-specific parametrization make their accuracy worth to be assessed on metal NPs as well.…”

Section: Introductionmentioning

confidence: 99%

Assessing Low-Cost Computational Methods against Structural Properties and Size Effects of Pt nanoparticles

Ricchebuono,

Vottero,

Piovano

et al. 2023

J. Phys. Chem. C

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An evaluation of the performances of several known low-cost methods for the reproduction of structural features of differently sized Pt nanoparticles (NPs) is presented. The full density functional theory PBE-dDsC functional (within the plane-wave formalism) was employed to benchmark the semiempirical tight-binding DFTB and GFNn-xTB (n = 0, 1, 2) and the reactive force-field ReaxFF. Performances were evaluated by comparing several size-dependent features (such as relative stabilities, structural descriptors, and vibrational features) computed with the different methods. Various structures (ordered and amorphous) and sizes (from Pt13 to Pt561) were considered in the datasets. ReaxFF molecular dynamics (MD) was employed to achieve the amorphization of cuboctahedral Pt147, Pt309, and Pt561 geometries, which were subsequently optimized with both the low-cost methods and the DFT reference, within a multilevel modeling approach. The structures were further annealed with GFN0-xTB MD. While DFTB performs quite well over all the selected structures, GFN2-xTB and the cheaper GFN0-xTB show a general predilection for amorphous geometries. The performances of GFN2-xTB are found to worsen with the increasing size of the system, while ReaxFF and GFN0-xTB undergo the opposite trend. We suggest that the semiempirical DFTB (and within certain limitations GFN0-xTB and ReaxFF) could be suited for fast screening through amorphous big-sized Pt NPs.

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Elucidating Structural and Electronic Features of PEO/(101)-TiO₂ Anatase Interfaces through First-Principles Metadynamics Simulations

Massaro,

Fasulo,

Muñoz-García

et al. 2024

J. Phys. Chem. C

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Structural and dynamic properties of the poly(ethylene oxide)/anatase interface (i.e., PEO/TiO 2 ) are explored via metadynamics simulations and density functional tight binding. 1-ns trajectories are reconstructed upon two different structurerelated collective variables: interfacial Ti surf −O PEO distances and polymer chain torsion angles. The conformational freedom of PEO is significantly influenced by multiple favorable interactions with unsaturated Ti sites on the anatase surface. From these trajectories, several equilibrium structures extracted from the free-energy surface are analyzed using electronic structure calculations within density functional theory: the titania work function results in being largely influenced by the dynamically resolved structuring of PEO on the anatase surface. Besides the intrinsic valuable insights into the technologically relevant PEO/TiO 2 interface, our findings provide the first innovative example of an affordable yet reliable computational protocol to describe a heterogeneous interface and predict the effects of molecular dynamics on relevant physicochemical properties.

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A DFTB-Based Molecular Dynamics Investigation of an Explicitly Solvated Anatase Nanoparticle

Cited by 6 publications

References 27 publications

Dynamics of Water Dissociative Adsorption on TiO₂ Anatase (101) at Monolayer Coverage and Below

Dynamics of Water Dissociative Adsorption on TiO₂ Anatase (101) at Monolayer Coverage and Below

Assessing Low-Cost Computational Methods against Structural Properties and Size Effects of Pt nanoparticles

Elucidating Structural and Electronic Features of PEO/(101)-TiO₂ Anatase Interfaces through First-Principles Metadynamics Simulations

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A DFTB-Based Molecular Dynamics Investigation of an Explicitly Solvated Anatase Nanoparticle

Cited by 6 publications

References 27 publications

Dynamics of Water Dissociative Adsorption on TiO2 Anatase (101) at Monolayer Coverage and Below

Dynamics of Water Dissociative Adsorption on TiO2 Anatase (101) at Monolayer Coverage and Below

Assessing Low-Cost Computational Methods against Structural Properties and Size Effects of Pt nanoparticles

Elucidating Structural and Electronic Features of PEO/(101)-TiO2 Anatase Interfaces through First-Principles Metadynamics Simulations

Contact Info

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Resources

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Dynamics of Water Dissociative Adsorption on TiO₂ Anatase (101) at Monolayer Coverage and Below

Dynamics of Water Dissociative Adsorption on TiO₂ Anatase (101) at Monolayer Coverage and Below

Elucidating Structural and Electronic Features of PEO/(101)-TiO₂ Anatase Interfaces through First-Principles Metadynamics Simulations