Investigation of hydrogen bonds and temperature effects on the water monolayer adsorption on rutile TiO2 (110) by first-principles molecular dynamics simulations

Density Functional Theory (DFT), based on both static and Born–Oppenheimer Molecular Dynamics approaches, has been used to investigate the effect of hydrogen bonds and temperature on the water monolayer adsorption on the rutile TiO2 (110) face. It was demonstrated that the difference between some previous theoretical results and experimental data is due to too slim slab thickness model and/or too small surface area. According to the present static calculations, water monolayer adsorbs molecularly on the five-fold titanium atoms of an optimised five-layer slab thickness, due to the stabilising lateral hydrogen bonds between molecules. From the molecular dynamics simulations, two adsorption mechanisms were described as a function of temperature. Finally, it was pointed out that the dynamics of water adsorption is strongly influenced by the structural model used. When temperature increases, the monolayer dissociates gradually. However, because of the periodic boundary conditions, the 1×1 surface unit needs to be extended to at least 2×5 to get an accurate representation of the monolayer dissociation ratio. In these conditions, this ratio is around 20%, 25% and 33% at 270, 350 and 425K, respectively. ► Ab initio Molecular Dynamics approach has been used to investigate hydrogen bonds and temperature effects on H2O adsorption on TiO2. ► From static calculations, water monolayer adsorbs molecularly on titanium atoms due to the stabilizing lateral hydrogen bonds. ► Two adsorption mechanisms were described as a function of temperature. ► When temperature increases, the monolayer dissociates gradually. ► The monolyer dissociation ratio is around 20 %, 25 % and 33 % at 270, 350 and 425 K, respectively.