TY - JOUR
T1 - Comment on "structure and dynamics of liquid water on rutile TiO 2(110)"
AU - Wesolowski, David J.
AU - Sofo, Jorge O.
AU - Bandura, Andrei V.
AU - Zhang, Zhan
AU - Mamontov, Eugene
AU - Předota, Milan
AU - Kumar, Nitin
AU - Kubicki, James D.
AU - Kent, Paul R.C.
AU - Vlcek, Lukas
AU - MacHesky, Michael L.
AU - Fenter, Paul A.
AU - Cummings, Peter T.
AU - Anovitz, Lawrence M.
AU - Skelton, Adam A.
AU - Rosenqvist, Jörgen
PY - 2012/4/5
Y1 - 2012/4/5
N2 - Liu and co-workers discussed the long-standing debate regarding whether H 2O molecules on the defect-free (110) surface of rutile (α-TiO 2) 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.
AB - Liu and co-workers discussed the long-standing debate regarding whether H 2O molecules on the defect-free (110) surface of rutile (α-TiO 2) 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.
UR - http://www.scopus.com/inward/record.url?scp=84860265468&partnerID=8YFLogxK
U2 - 10.1103/PhysRevB.85.167401
DO - 10.1103/PhysRevB.85.167401
M3 - Review article
AN - SCOPUS:84860265468
SN - 1098-0121
VL - 85
JO - Physical Review B - Condensed Matter and Materials Physics
JF - Physical Review B - Condensed Matter and Materials Physics
IS - 16
M1 - 167401
ER -