Ab initio periodic Hartree-Fock calculations for interpretation of the scanning tunneling microscope (STM) images of graphite

Journal of Physical Chemistry B

Volumn 102, Issue 31, 1998, Pages 6020-6024

  Lee, Kee Hag ^a   Causa M ^b   Park, Sung Soo ^a  

^a Wonkwang University   (South Korea)

^b UNIVERSITY OF TURIN   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001634977     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp980639d     Document Type: Article

References (28)

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22. The periodic Hartree-Fock (PHF) method systematically expands the band structure, whereas the density functional theory (DFT) systematically underestimates band gaps and bandwidths. We calculated with our program both PHF and DFT and found qualitative agreements in the band structure for the two methods. We also found a qualitative agreement of the asymmetry in the charge density on sites A and B of graphite. Dovesi, R.; Saunders: V. R.; Roetti, C.; Causá, M.; Harrison, N. M.; Orlando, R.; Aprá, E. CRYSTAL95 User's Manual; University of Torino: Torino, Italy, 1996.
23. We checked the stability of our results with the basis set, changing the external exponent in the range 0.19-0.27. We confirmed that the best exponent is 0.24, and the STM images have no difference in the interval 0.21-0.25. So, we have reasonably reproduced the decay of the density perpendicularly to the surface. The linear combination of atomic Orbitals periodic calculations cannot use diffuse basis sets because the real basis is the set of block functions built over the atomic orbitals: too wide functions give linear dependence between the block functions. Gordon, M. S.; Binkley, J. S.; Pople, J. A.; Pietro, W. J.; Hehre, W. J. J. Am. Chem. Soc. 1982, 104, 2797.
24. Our results are stable with the number of layers in the slab. We explored slabs composed of 2, 3, 4, and 5 graphite layers. The physical origin of the asymmetry in the graphite STM images is in the exchange short-range repulsion between the layers. Even a two-layer slab shows this interaction.
25. Our results are stable with respect to the integration in the k space. We also obtain the same STM image using 2304 k points in the primary net and 20 736 k points in the interpolated net that we used for calculating the occupied fraction of the Brillouin zone for each energy value.
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