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This content will become publicly available on January 11, 2017

Title: Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO2(111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H+) were identified on stoichiometric and oxygen-deficient CeO2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states. Moreover, the most favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.
 [1] ;  [2] ;  [3] ;  [4]
  1. Shaanxi Normal Univ. (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Shaanxi Normal Univ. (China)
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 1932-7447
Grant/Contract Number:
201303004; GK:201101004; AC52-06NA25396; 21173139; 2013KCT-17
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 5; Journal ID: ISSN 1932-7447
American Chemical Society
Research Org:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States