An accurate first-principles treatment of complex systems, such as surfaces, continues to be a major challenge in computational chemistry. A popular approach to treat such systems is the use of cluster models, where a moderately sized model system is constructed by excising a cluster from the extended surface. This requires cutting chemical bonds, creating dangling bonds on the cluster boundary atoms that can introduce unphysical errors. Pseudobond, pseudoatom, and quantum capping potential approaches have been developed to treat such systems using a boundary “design-atom” subject to an appropriately fitted effective potential. However, previous approaches have been developed only for truncation of a single covalent bond. They may not be adequate for many important problems involving surface chemistry or materials chemistry, where multiple covalent bonds are severed between layers. In this paper, we have extended the pseudoatom formulation for divalent silicon, which can be employed to describe accurate Si(100) surface chemistry. The effective core potential parameters of our pseudoatom are obtained by fitting to geometrical parameters and atomic charges of molecules containing Si–Si and Si–O bonds, making our pseudoatom robust for applicability in different bonding environments. We calibrate the performance of our pseudoatom approach in small molecules and surface models, and also discuss its ability to describe heteroatomic bonds using multiple theoretical methods.
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28 October 2013
Research Article|
October 25 2013
Divalent pseudoatoms for modeling Si(100) surfaces
Benjamin C. Gamoke;
Benjamin C. Gamoke
Department of Chemistry,
Indiana University
, Bloomington, Indiana 47405, USA
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Ujjal Das;
Ujjal Das
a)
Department of Chemistry,
Indiana University
, Bloomington, Indiana 47405, USA
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Hrant P. Hratchian;
Hrant P. Hratchian
b)
Department of Chemistry,
Indiana University
, Bloomington, Indiana 47405, USA
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Krishnan Raghavachari
Krishnan Raghavachari
c)
Department of Chemistry,
Indiana University
, Bloomington, Indiana 47405, USA
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a)
Present address: Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
b)
Present address: School of Natural Sciences, University of California, Merced, California 95343, USA.
c)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 139, 164708 (2013)
Article history
Received:
August 05 2013
Accepted:
October 03 2013
Citation
Benjamin C. Gamoke, Ujjal Das, Hrant P. Hratchian, Krishnan Raghavachari; Divalent pseudoatoms for modeling Si(100) surfaces. J. Chem. Phys. 28 October 2013; 139 (16): 164708. https://doi.org/10.1063/1.4825402
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