Hardcastle, TP, Seabourne, CR, Brydson, RMD et al. (2 more authors) (2013) The energy of step defects on the TiO2 rutile (110) surface: An ab initio DFT methodology. Journal of Physical Chemistry Part C: Nanomaterials and Interfaces, 117 (45). 23766 - 23780. ISSN 1932-7447
Abstract
We present a novel methodology for dealing with quantum size effects (QSE) when calculating the energy per unit length and step–step interaction energy of atomic step defects on crystalline solid surfaces using atomistic slab models. We apply it to the TiO2 rutile (110) surface using density functional theory (DFT) for which it is well-known that surface energies converge in a slow and oscillatory manner with increasing slab size. This makes it difficult to reliably calculate step energies because they are very sensitive to supercell surface energies, and yet the surface energies depend sensitively on the choice of slab chemical formula due to the dominance of QSE at computationally practical slab sizes. The commonly used method of calculating surface energies by taking the intercept of a best fit line of total supercell energies against slab size breaks down and becomes highly unreliable for such systems. Our systematic approach, which can be applied to any crystalline surface, bypasses such statistical estimation techniques and cross checks and makes robust what is otherwise a very unreliable process of extracting the energies of steps. We use the calculated step energies to predict island shapes on rutile (110) which compare favorably with published scanning tunneling microscopy (STM) images.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2013, American Chemical Society. This is an author produced version of a paper published in Journal of Physical Chemistry Part C. Uploaded with permission from the publisher. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) > Institute for Materials Research (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 02 Dec 2013 12:07 |
Last Modified: | 24 Apr 2017 15:23 |
Published Version: | http://dx.doi.org/10.1021/jp4078135 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/jp4078135 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:77087 |