Introduction Computational Details Our Results Summary

Adsorption characteristics of Thiophene on Cu and

Ni(100): role of van der Waals
Tomas Rojas
1
, Jeronimo Matos
1
, Abdelkader Kara
1
1
Physics Department, University of Central Florida
American Physical Society, March Meeting, 2014
Introduction Computational Details Our Results Summary
1
Introduction
Motivation
Experimental Results
2
Computational Details
Calculation Details
Adsorption Geometries
3
Our Results
Adsorption Energies
Adsorption Heights
Changes Electronic Structure
Charge Redistribution
Introduction Computational Details Our Results Summary
Motivation
Thiophene (C
4
H
4
S) is a at 5-membered ring, aromatic
molecule.
Density functional theory (DFT) framework did not include
vdW interaction until very recently.
The main purpose is to evaluate its performance in the
adsorption of organic molecules over metallic substrates using
vdW-dF.
Cu (coinage metal) and Ni (reactive magnetic metal).
Experimental Research on Au(111), Cu[(100), (110)] , Pd
[(100), (111)] , Ni(100), Pt [ (111), (100) ].
Computational Research on Cu(100), Ni(100) and Pd(100).
Introduction Computational Details Our Results Summary
Experimental Results
1
Imanishi, A., Yagi, S., & Yokoyama, T. (1996). Journal of Electron
. . . , 80, 151154.
Introduction Computational Details Our Results Summary
Calculation Details
Vienna Ab-initio Simulation Package (VASP)
1
Five vdW functionals: optB86b, optB88, optPBE, revPBE
and rPW86. And their comparision with PBE.
23
Substrates (100): 45 atom, 5 layer slab using periodic
boundary conditions and a minimum of 21 of vacuum.
The brillouin zone is sampled using 6x6x1 k-point meshes.
Structural optimization is performed for the molecule and
substrate separately, followed by a relaxation of the combined
system with the last two layers of the substrate xed.
1
G. Kresse and J. Furthmuller, Phys. Rev. B 54,11169 (1996).
2
J. Klime, D. Bowler, and A. Michaelides, (2011). Phys. Rev. B83(19),
195131.
3
M. Dion et al. (2004). Phys. Rev. Letters, 92(24), 246401.
Introduction Computational Details Our Results Summary
Adsorption Geometries
Atop 0 Bridge 0 Hollow 0
Atop 45 Bridge 45 Hollow 45
Introduction Computational Details Our Results Summary
Adsorption Energies
Binding Energies
E
ad
= E
Molecule
+E
Substrate
E
Molecule/Substrate
Introduction Computational Details Our Results Summary
Adsorption Heights
Adsorption Heights
Distance between the S atom and the closest metallic atom.
Imanishi, A., Yagi, S., & Yokoyama, T. (1996). Journal of Electron . . . , 80, 151154.
Introduction Computational Details Our Results Summary
Adsorption Heights
C-S distance
Distance between the S atom and the next C atom.
Imanishi, A., Yagi, S., & Yokoyama, T. (1996). Journal of Electron . . . , 80, 151154.
Introduction Computational Details Our Results Summary
Changes Electronic Structure
Partial Density of States dz
2
- Cu
The dz
2
is the most favorable to couple with the pz orbital of the
sulfur atom.
Atom 4
Introduction Computational Details Our Results Summary
Changes Electronic Structure
Partial Density of States dz
2
- Ni
The dz
2
is the most favorable to couple with the pz orbital of the
sulfur atom.
Atom 4
Introduction Computational Details Our Results Summary
Charge Redistribution
Charge redistribution on Copper
!"#$%&' )*+,$-
uepleuon
Accumulauon
lsosurface 1.34 10
-3
e A
-3

Introduction Computational Details Our Results Summary
Charge Redistribution
Charge Transfer (Bader Analysis)
Substrate Charge Transfer
4
(e

)
Cu < 0.14
Ni < 0.25
4
Tang, W., Sanville, E., & Henkelman, G. (2009). Condensed Matter : An
Institute of Physics Journal, 21(8), 084204.
Introduction Computational Details Our Results Summary
Charge Redistribution
Ni Bridge 45
5 6
Rupture of the aromatic ring may have inuence in the charge
tranfer measurements.
5
Orita, H., & Itoh, N. (2004). Surface Science, 550(1-3), 177184.
6
Mittendorfer, F., & Hafner, J. (2001). Surface Science, 492(1-2), 2733.
Introduction Computational Details Our Results Summary
Summary
Opt-type functionals strongly enhance the adsorption
energies, and reduce the adsorption heights on all surfaces.
Changes in the binding energies on Ni are signicantly higher
than Cu.
revPBE and rPW86 functionals also increase the adsorption
energies, less strongly than the opt-type functionals, and only
for coinage metals. This results from strong repulsive
character at short distances.
Charge redistribution is enhanced by opt-type compared to
revPBE and rPW86 functionals.
Introduction Computational Details Our Results Summary
Poster Session
Session H1: Poster Session II (14:00 - 17:00) 2:00 PM,
Tuesday, March 4, 2014 Room: Exhibit Hall F
Abstract: An extensive computational study of the
adsorption of thiophene on transition metal surfaces:
role of van der Waals
Authors: Tomas Rojas (Department of Physics, University of
Central Florida), Abdelkader Kara (Department of Physics,
University of Central Florida)
Introduction Computational Details Our Results Summary
Acknowledgements
This work was made possible by funding from the U.S.
Department of Energy Grant No. DE-FG02-11ER16243
The calculations were conducted using computational
resources from NERSC
Travel to the APS March Meeting made possible by funding
from UCF College of Graduate Studies and UCF Student
Government.
Thank you to Dr. Handan Yildirim for helpful discussions and
guidance.
Thank you for your attention!