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

David J. Wesolowski, Jorge O. Sofo, Andrei V. Bandura, Zhan Zhang, Eugene Mamontov, Milan Předota, Nitin Kumar, James D. Kubicki, Paul R. C. Kent, Lukas Vlcek, Michael L. Machesky, Paul A. Fenter, Peter T. Cummings, Lawrence M. Anovitz, Adam A. Skelton, and Jörgen Rosenqvist
Phys. Rev. B 85, 167401 – Published 5 April 2012

Abstract

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 (α-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 published work, 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.

  • Received 12 February 2011

DOI:https://doi.org/10.1103/PhysRevB.85.167401

©2012 American Physical Society

Authors & Affiliations

David J. Wesolowski1, Jorge O. Sofo2, Andrei V. Bandura3, Zhan Zhang4, Eugene Mamontov1, Milan Předota5, Nitin Kumar2, James D. Kubicki2, Paul R. C. Kent1, Lukas Vlcek1, Michael L. Machesky6, Paul A. Fenter4, Peter T. Cummings7, Lawrence M. Anovitz1, Adam A. Skelton7, and Jörgen Rosenqvist8

  • 1Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA
  • 2The Pennsylvania State University, University Park, Pennsylvania 16802, USA
  • 3St. Petersburg State University, St. Petersburg, Russia
  • 4Argonne National Laboratory, Argonne, Illinois 60439, USA
  • 5University of South Bohemia, České Budějovice 370 05, Czech Republic
  • 6Illinois State Water Survey, Champaign, Illinois 61820, USA
  • 7Vanderbilt University, Nashville, Tennessee 37235, USA
  • 8University of Leeds, Leeds LS2 9JT, United Kingdom

Comments & Replies

Reply to “Comment on `Structure and dynamics of liquid water on rutile TiO2(110)' ”

Li-Min Liu, C. Zhang, G. Thornton, and A. Michaelides
Phys. Rev. B 85, 167402 (2012)

Article Text (Subscription Required)

Click to Expand

Original Article

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

Li-Min Liu, Changjun Zhang, Geoff Thornton, and Angelos Michaelides
Phys. Rev. B 82, 161415(R) (2010)

References (Subscription Required)

Click to Expand
Issue

Vol. 85, Iss. 16 — 15 April 2012

Reuse & Permissions
Access Options
Author publication services for translation and copyediting assistance advertisement

Authorization Required


×
×

Images

×

Sign up to receive regular email alerts from Physical Review B

Log In

Cancel
×

Search


Article Lookup

Paste a citation or DOI

Enter a citation
×