A water/(101) anatase TiO2 interface has been investigated with the DFT-based self-consistent-charge density functional tight-binding theory (SCC-DFTB). By comparison of the computed structural, energetic, and dynamical properties with standard DFT-GGA and experimental data, we assess the accuracy of SCC-DFTB for this prototypical solid-liquid interface. We tested different available SCC-DFTB parameters for Ti-containing compounds and, accordingly, combined them to improve the reliability of the method. To better describe water energetics, we have also introduced a modified hydrogen-bond-damping function (HBD). With this correction, equilibrium structures and adsorption energies of water on (101) anatase both for low (0.25 ML) and full (1 ML) coverages are in excellent agreement with those obtained with a higher level of theory (DFT-GGA). Furthermore, Born-Oppenheimer molecular dynamics (MD) simulations for mono-, bi-, and trilayers of water on the surface, as computed with SCC-DFTB, evidence similar ordering and energetics as DFT-GGA Car-Parrinello MD results. Finally, we have evaluated the energy barrier for the dissociation of a water molecule on the anatase (101) surface. Overall, the combined set of parameters with the HBD correction (SCC-DFTB+HBD) is shown to provide a description of the water/water/titania interface, which is very close to that obtained by standard DFT-GGA, with a remarkably reduced computational cost. Hence, this study opens the way to the future investigations on much more extended and realistic TiO2/liquid water systems, which are extremely relevant for many modern technological applications

Selli, D., Fazio, G., Seifert, G., DI VALENTIN, C. (2017). Water Multilayers on TiO2 (101) Anatase Surface: Assessment of a DFTB-Based Method. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 13(8), 3862-3873 [10.1021/acs.jctc.7b00479].

Water Multilayers on TiO2 (101) Anatase Surface: Assessment of a DFTB-Based Method

SELLI, DANIELE
Primo
;
FAZIO, GIANLUCA
Secondo
;
DI VALENTIN, CRISTIANA
2017

Abstract

A water/(101) anatase TiO2 interface has been investigated with the DFT-based self-consistent-charge density functional tight-binding theory (SCC-DFTB). By comparison of the computed structural, energetic, and dynamical properties with standard DFT-GGA and experimental data, we assess the accuracy of SCC-DFTB for this prototypical solid-liquid interface. We tested different available SCC-DFTB parameters for Ti-containing compounds and, accordingly, combined them to improve the reliability of the method. To better describe water energetics, we have also introduced a modified hydrogen-bond-damping function (HBD). With this correction, equilibrium structures and adsorption energies of water on (101) anatase both for low (0.25 ML) and full (1 ML) coverages are in excellent agreement with those obtained with a higher level of theory (DFT-GGA). Furthermore, Born-Oppenheimer molecular dynamics (MD) simulations for mono-, bi-, and trilayers of water on the surface, as computed with SCC-DFTB, evidence similar ordering and energetics as DFT-GGA Car-Parrinello MD results. Finally, we have evaluated the energy barrier for the dissociation of a water molecule on the anatase (101) surface. Overall, the combined set of parameters with the HBD correction (SCC-DFTB+HBD) is shown to provide a description of the water/water/titania interface, which is very close to that obtained by standard DFT-GGA, with a remarkably reduced computational cost. Hence, this study opens the way to the future investigations on much more extended and realistic TiO2/liquid water systems, which are extremely relevant for many modern technological applications
Articolo in rivista - Articolo scientifico
DFTB; Titanium dioxide; Anatase; Solid – Liquid Interface; Water Adsorption; Hydrogen Bond; Molecular Dynamics
English
2017
13
8
3862
3873
open
Selli, D., Fazio, G., Seifert, G., DI VALENTIN, C. (2017). Water Multilayers on TiO2 (101) Anatase Surface: Assessment of a DFTB-Based Method. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 13(8), 3862-3873 [10.1021/acs.jctc.7b00479].
File in questo prodotto:
File Dimensione Formato  
Selli-2017-J Chem Theory Comput-VoR.pdf

accesso aperto

Descrizione: Article
Tipologia di allegato: Publisher’s Version (Version of Record, VoR)
Dimensione 2.79 MB
Formato Adobe PDF
2.79 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/168374
Citazioni
  • Scopus 41
  • ???jsp.display-item.citation.isi??? 40
Social impact