Comment on "Structure and dynamics of liquid water on rutile TiO2(110)

Journal Article · Sun Jan 01 04:00:00 EST 2012 · Physical Review B

DOI:https://doi.org/10.1103/PhysRevB.85.167401· OSTI ID:1045880

Wesolowski, David J ^[1]; Sofo, Jorge O. ^[2]; Bandura, Andrei V. ^[3]; Zhang, Zhan ^[4]; Mamontov, Eugene ^[1]; Predota, M. ^[5]; Kumar, Nitin ^[1]; Kubicki, James D. ^[2]; Kent, Paul R ^[1]; Vlcek, Lukas ^[1]; Machesky, Michael L. ^[6]; Fenter, Paul ^[4]; Cummings, Peter T ^[1]; Skelton, A A ^[7]; Rosenqvist, Jorgen K ^[1]

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1. ORNL
2. Pennsylvania State University
3. St. Petersburg State University, St. Petersburg, Russia
4. Argonne National Laboratory (ANL)
5. University of South Bohemia, Czech Republic
6. Illinois State Water Survey, Champaign, IL
7. Vanderbilt University

Liu and co-workers [Phys. Rev. B 82, 161415 (2010)] discussed the long-standing debate regarding whether H2O molecules on the defect-free (110) surface of rutile ( -TiO2) sorb associatively, or there is dissociation of some or all first-layer water to produce hydroxyl surface sites. They conducted static density functional theory (DFT) and DFT molecular dynamics (DFT-MD) investigations using a range of cell configurations and functionals. We have reproduced their static DFT calculations of the influence of crystal slab thickness on water sorption energies. However, we disagree with several assertions made by these authors: (a) that second-layer water structuring and hydrogen bonding to surface oxygens and adsorbed water molecules are weak ; (b) that translational diffusion of water molecules in direct contact with the surface approaches that of bulk liquid water; and (c) that there is no dissociation of adsorbed water at this surface in contact with liquid water. These assertions directly contradict our publishedwork, which compared synchrotron x-ray crystal truncation rod, second harmonic generation, quasielastic neutron scattering, surface charge titration, and classical MD simulations of rutile (110) single-crystal surfaces and (110)-dominated powders in contact with bulk water, and (110)-dominated rutile nanoparticles with several monolayers of adsorbed water.

• Research Organization: Oak Ridge National Laboratory (ORNL)
• Sponsoring Organization: SC USDOE - Office of Science (SC)
• DOE Contract Number: AC05-00OR22725
• OSTI ID: 1045880
• Journal Information: Physical Review B, Journal Name: Physical Review B Journal Issue: 16 Vol. 85; ISSN 1098-0121
• Country of Publication: United States
• Language: English

Related Subjects

08 HYDROGEN
BONDING
DIFFUSION
DISSOCIATION
FUNCTIONALS
HARMONIC GENERATION
HYDROGEN
NEUTRONS
RUTILE
SCATTERING
SORPTION
SYNCHROTRONS
THICKNESS
TITRATION
WATER