M. Gajdo?, A. Eichler, and J. Hafner, calculations, Journal of Physics: Condensed Matter, vol.16, issue.8, p.1141, 2004.
DOI : 10.1088/0953-8984/16/8/001

M. Meier, surface, Physical Review B, vol.87, issue.8, p.85414, 2015.
DOI : 10.1103/PhysRevB.84.085411

URL : https://hal.archives-ouvertes.fr/cea-00371815

M. Meier, and (100) surfaces: Influence of bonding strength and annealing temperature on surface terminations, Physical Review B, vol.64, issue.7, p.75412, 2016.
DOI : 10.1016/S0039-6028(98)00363-X

URL : https://hal.archives-ouvertes.fr/hal-01284776

F. Stein, M. Palm, and G. Sauthoff, Structure and stability of Laves phases. Part I. Critical assessment of factors controlling Laves phase stability, Intermetallics, vol.12, issue.7-9, p.713, 2004.
DOI : 10.1016/j.intermet.2004.02.010

G. Trambly-de-laissardière, D. Nguyen-manh, and D. Mayou, Electronic structure of complex Hume-Rothery phases and quasicrystals in transition metal aluminides, Progress in Materials Science, vol.50, issue.6, p.679, 2005.
DOI : 10.1016/j.pmatsci.2005.01.001

U. Mizutani, Introduction to the electron theory of metals, 2003.
DOI : 10.1017/CBO9780511612626

N. F. Mott and H. Jones, The theory of the properties of metals and alloys, 1936.

J. Dubois, Properties- and applications of quasicrystals and complex metallic alloys, Chemical Society Reviews, vol.51, issue.95, p.6760, 2012.
DOI : 10.1002/ijch.201100149

M. Mihalkovi?, H. Elhor, and J. Suck, Atomic dynamics in Al-rich Al-Co alloys near the composition of the decagonal quasicrystal, Physical Review B, vol.23, issue.207, p.214301, 2001.
DOI : 10.1107/S0365110X67002439

K. Sugiyama, S. Nishimura, and K. Hiraga, Structure of a W???(AlCoNi) crystalline phase related to Al???Co???Ni decagonal quasicrystals, studied by single crystal X-ray diffraction, Journal of Alloys and Compounds, vol.342, issue.1-2, p.65, 2002.
DOI : 10.1016/S0925-8388(02)00135-4

E. Belin-ferré, Electronic structure of hexagonal, Journal of Physics: Condensed Matter, vol.9, issue.44, p.9585, 1997.
DOI : 10.1088/0953-8984/9/44/013

K. Yamamoto, M. Jono, and Y. Matsuo, X-ray study of the electron density distributions for hexagonal and, Journal of Physics: Condensed Matter, vol.11, issue.4, p.1015, 1999.
DOI : 10.1088/0953-8984/11/4/009

A. Ormeci and Y. Grin, Chemical Bonding in Al5Co2: The Electron Localizability-Electron Density Approach, Israel Journal of Chemistry, vol.12, issue.11-12, p.1349, 2011.
DOI : 10.1016/j.intermet.2004.01.006

M. Mihalkovi? and M. Widom, binary alloy system, Physical Review B, vol.213, issue.6, p.14207, 2007.
DOI : 10.1103/PhysRevLett.77.3865

U. Burkhardt, M. Ellner, Y. Grin, and B. Baumgartner, Powder diffraction refinement of the Co2Al5 structure, Powder Diffraction, vol.64, issue.03, p.159, 1998.
DOI : 10.3891/acta.chem.scand.21-0647

F. Stein, C. He, and N. Dupin, Melting behaviour and homogeneity range of B2 CoAl and updated thermodynamic description of the Al???Co system, Intermetallics, vol.39, p.58, 2013.
DOI : 10.1016/j.intermet.2013.03.011

A. Mayer, H. Salopaasi, K. Pussi, and R. Diehl, A novel method for the extraction of intensity???energy spectra from low-energy electron diffraction patterns, Computer Physics Communications, vol.183, issue.7, p.1443, 2012.
DOI : 10.1016/j.cpc.2012.02.019

J. B. Pendry, Reliability factors for LEED calculations, Journal of Physics C: Solid State Physics, vol.13, issue.5, p.937, 1980.
DOI : 10.1088/0022-3719/13/5/024

M. Meier, surface, Physical Review B, vol.87, issue.8, p.85414, 2015.
DOI : 10.1103/PhysRevB.84.085411

URL : https://hal.archives-ouvertes.fr/cea-00371815

S. A. Villaseca, Complex Metallic Alloy, The Journal of Physical Chemistry C, vol.115, issue.30, p.14922, 2011.
DOI : 10.1021/jp203727h

URL : https://hal.archives-ouvertes.fr/hal-00974222

P. Hohenberg and W. Kohn, Inhomogeneous Electron Gas, Physical Review, vol.80, issue.3B, p.864, 1964.
DOI : 10.1088/0370-1328/80/5/307

W. Kohn and L. J. Sham, Self-Consistent Equations Including Exchange and Correlation Effects, Physical Review, vol.119, issue.4A, p.1133, 1965.
DOI : 10.1103/PhysRev.119.1153

G. Kresse and J. Hafner, molecular dynamics for liquid metals, Physical Review B, vol.41, issue.1, p.558, 1993.
DOI : 10.1103/PhysRevB.41.1497

A. Benali, C. Lacaze-dufaure, and J. Morillo, Density functional study of copper segregation in aluminum, Surface Science, vol.605, issue.3-4, p.341, 2011.
DOI : 10.1016/j.susc.2010.10.040

URL : https://hal.archives-ouvertes.fr/hal-00842550

P. H. Philipsen and E. J. Baerends, transition metals: Density functional theory atomic and bulk calculations, Physical Review B, vol.98, issue.8, p.5326, 1996.
DOI : 10.1063/1.464985

T. C. Leung, C. T. Chan, and B. N. Harmon, Ground-state properties of Fe, Co, Ni, and their monoxides: Results of the generalized gradient approximation, Physical Review B, vol.27, issue.7, p.2923, 1991.
DOI : 10.1103/PhysRevB.27.6964

A. V. Ruban, Surface composition of ordered alloys:??????An off-stoichiometric effect, Physical Review B, vol.25, issue.17, p.174201, 2002.
DOI : 10.1002/(SICI)1096-9918(199703)25:3<177::AID-SIA219>3.0.CO;2-T

P. E. Blochl, Projector augmented-wave method, Physical Review B, vol.44, issue.24, p.17953, 1994.
DOI : 10.1103/PhysRevB.44.13063

K. Momma and F. Izumi, for three-dimensional visualization of crystal, volumetric and morphology data, Journal of Applied Crystallography, vol.51, issue.6, p.1272, 2011.
DOI : 10.1107/S0108767394013292

W. A. Hofer and J. Redinger, Scanning tunneling microscopy of binary alloys: first principles calculation of the current for PtX (100) surfaces., Surface Science, vol.447, issue.1-3, p.51, 2000.
DOI : 10.1016/S0039-6028(99)01053-5

A. Togo, F. Oba, and I. Tanaka, at high pressures, Physical Review B, vol.192, issue.193, p.134106, 2008.
DOI : 10.1007/s002690000092

S. Andrieu and P. Müller, Les surfaces solides: concepts et méthodes, 2012.

F. Bechstedt, Principles of surface physics, 2003.
DOI : 10.1007/978-3-642-55466-7

G. Tréglia, Alloy surfaces: segregation, reconstruction and phase transitions, Computational Materials Science, vol.15, issue.2, p.196, 1999.
DOI : 10.1016/S0927-0256(99)00004-X

M. Mihalkovi? and M. Widom, : First-principles total energy and phonon calculations, Physical Review B, vol.85, issue.1, p.14113, 2012.
DOI : 10.1209/0295-5075/32/9/005

G. Henkelman, B. P. Uberuaga, and H. Jónsson, A climbing image nudged elastic band method for finding saddle points and minimum energy paths, The Journal of Chemical Physics, vol.13, issue.22, p.9901, 2000.
DOI : 10.1103/PhysRevLett.85.618

G. Henkelman and H. Jónsson, Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points, The Journal of Chemical Physics, vol.82, issue.22, p.9978, 2000.
DOI : 10.1063/1.475306

M. Kraj?í and J. Hafner, : Ga Enrichment Improves Selectivity, The Journal of Physical Chemistry C, vol.118, issue.23, p.12285, 2014.
DOI : 10.1021/jp5025075

S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction, Journal of Computational Chemistry, vol.10, issue.15, p.1787, 2006.
DOI : 10.1007/s002140050244

U. Burkhardt, M. Ellner, Y. Grin, and B. Baumgartner, Powder diffraction refinement of the Co2Al5 structure, Powder Diffraction, vol.64, issue.03, p.159, 1998.
DOI : 10.3891/acta.chem.scand.21-0647

M. Mihalkovi? and M. Widom, binary alloy system, Physical Review B, vol.213, issue.6, p.14207, 2007.
DOI : 10.1103/PhysRevLett.77.3865

M. Hagen and M. W. Finnis, Point defects and chemical potentials in ordered alloys, Philosophical Magazine A, vol.11, issue.2, p.447, 1998.
DOI : 10.1016/1359-6454(96)00117-6

A. Ormeci and Y. Grin, Chemical Bonding in Al5Co2: The Electron Localizability-Electron Density Approach, Israel Journal of Chemistry, vol.12, issue.11-12, p.1349, 2011.
DOI : 10.1016/j.intermet.2004.01.006

G. Trambly-de-laissardière, D. Nguyen-manh, and D. Mayou, Electronic structure of complex Hume-Rothery phases and quasicrystals in transition metal aluminides, Progress in Materials Science, vol.50, issue.6, p.679, 2005.
DOI : 10.1016/j.pmatsci.2005.01.001

E. Belin-ferré, Electronic structure of hexagonal, Journal of Physics: Condensed Matter, vol.9, issue.44, p.9585, 1997.
DOI : 10.1088/0953-8984/9/44/013

M. Mihalkovi?, H. Hellnor, and J. B. Suck, Atomic dynamics in Al-rich Al-Co alloys near the composition of the decagonal quasicrystal, Physical Review B, vol.23, issue.207, p.214301, 2001.
DOI : 10.1107/S0365110X67002439

M. Meier, surface, Physical Review B, vol.87, issue.8, p.85414, 2015.
DOI : 10.1103/PhysRevB.84.085411

URL : https://hal.archives-ouvertes.fr/cea-00371815

H. Shin, studies, Physical Review B, vol.86, issue.8, p.85411, 2011.
DOI : 10.1103/PhysRevB.69.153404

URL : https://hal.archives-ouvertes.fr/hal-01157637

J. Ledieu, Catalyst, Physical Review Letters, vol.110, issue.7, p.76102, 2013.
DOI : 10.1088/0953-8984/22/8/084022

URL : https://hal.archives-ouvertes.fr/hal-00977979

T. Tanabe, S. Kameoka, and A. P. Tsai, Microstructure of leached Al-Cu-Fe quasicrystal with high catalytic performance for steam reforming of methanol, Applied Catalysis A: General, vol.384, issue.1-2, p.241, 2010.
DOI : 10.1016/j.apcata.2010.06.045

J. Ledieu, ´. E. Gaudry, V. Fournée, and . Sci, Surfaces of Al-based complex metallic alloys: atomic structure, thin film growth and reactivity, Science and Technology of Advanced Materials, vol.37, issue.3, p.34802, 2014.
DOI : 10.1016/j.apsusc.2013.06.101

URL : https://hal.archives-ouvertes.fr/hal-01075798

S. Song and E. R. Ryba, Structural repeat units and repeat schemes for the Al-Cu-Co decagonal phase and its crystalline approximants, Philosophical Magazine Letters, vol.65, issue.2, p.85, 1992.
DOI : 10.1111/j.1365-2818.1987.tb01353.x

G. Trambly-delaissardì-ere, D. Nguyen-manh, and D. Mayou, Electronic structure of complex Hume-Rothery phases and quasicrystals in transition metal aluminides, Progress in Materials Science, vol.50, issue.6, p.679, 2005.
DOI : 10.1016/j.pmatsci.2005.01.001

A. Ormeci and Y. Grin, Chemical Bonding in Al5Co2: The Electron Localizability-Electron Density Approach, Israel Journal of Chemistry, vol.12, issue.11-12, p.1349, 2011.
DOI : 10.1016/j.intermet.2004.01.006

U. Burkhardt, M. Ellner, Y. Grin, and B. Baumgartner, Powder diffraction refinement of the Co2Al5 structure, Powder Diffraction, vol.64, issue.03, p.159, 1998.
DOI : 10.3891/acta.chem.scand.21-0647

S. A. Villaseca, J. M. Dubois, and . Gaudry, complex metallic alloy, Philosophical Magazine, vol.13, issue.19-21, p.2894, 2011.
DOI : 10.1103/PhysRevLett.50.1998

URL : https://hal.archives-ouvertes.fr/hal-00974222

F. Stein, C. He, and N. Dupin, Melting behaviour and homogeneity range of B2 CoAl and updated thermodynamic description of the Al???Co system, Intermetallics, vol.39, p.58, 2013.
DOI : 10.1016/j.intermet.2013.03.011

A. Mayer, H. Salopaasi, K. Pussi, and R. Diehl, A novel method for the extraction of intensity???energy spectra from low-energy electron diffraction patterns, Computer Physics Communications, vol.183, issue.7, p.1443, 2012.
DOI : 10.1016/j.cpc.2012.02.019

J. B. Pendry and J. Phys, C: Solid State Phys, p.937, 1980.

G. Kresse and J. Hafner, molecular dynamics for liquid metals, Physical Review B, vol.41, issue.1, p.558, 1993.
DOI : 10.1103/PhysRevB.41.1497

G. Kresse and J. Hafner, molecular-dynamics simulation of the liquid-metal???amorphous-semiconductor transition in germanium, Physical Review B, vol.48, issue.20, p.14251, 1994.
DOI : 10.1103/PhysRevB.48.13115

G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Computational Materials Science, vol.6, issue.1, p.15, 1996.
DOI : 10.1016/0927-0256(96)00008-0

G. Kresse and J. Furthmüller, total-energy calculations using a plane-wave basis set, Physical Review B, vol.2, issue.16, p.11169, 1996.
DOI : 10.1007/978-3-642-83058-7

P. E. Blochl, Projector augmented-wave method, Physical Review B, vol.44, issue.24, p.17953, 1994.
DOI : 10.1103/PhysRevB.44.13063

G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Physical Review B, vol.9, issue.3, p.1758, 1999.
DOI : 10.1103/PhysRevB.55.13479

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Physical Review Letters, vol.80, issue.18, p.3865, 1996.
DOI : 10.1063/1.446965

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)], Physical Review Letters, vol.78, issue.7, p.1396, 1997.
DOI : 10.1103/PhysRevLett.78.1396

K. Momma and F. Izumi, for three-dimensional visualization of crystal, volumetric and morphology data, Journal of Applied Crystallography, vol.51, issue.6, p.1272, 2011.
DOI : 10.1107/S0108767394013292

M. Hagen and M. W. Finnis, Point defects and chemical potentials in ordered alloys, Philosophical Magazine A, vol.11, issue.2, p.447, 1998.
DOI : 10.1016/1359-6454(96)00117-6

C. Colinet and J. Tedenac, First principles calculations in V???Si system. Defects in A15-V3Si phase, Computational Materials Science, vol.85, p.94, 2014.
DOI : 10.1016/j.commatsci.2013.12.044

URL : https://hal.archives-ouvertes.fr/hal-00997655

A. Togo, F. Oba, and I. Tanaka, at high pressures, Physical Review B, vol.192, issue.193, p.134106, 2008.
DOI : 10.1007/s002690000092

R. Mittal, M. Zbiri, H. Schober, E. Marelli, S. J. Hibble et al., calculations, Physical Review B, vol.60, issue.2, p.24301, 2011.
DOI : 10.1021/ja073791e

N. Moll, A. Kley, E. Pehlke, and M. Scheffler, GaAs equilibrium crystal shape from first principles, Physical Review B, vol.34, issue.12, p.8844, 1996.
DOI : 10.1103/PhysRevLett.52.1911

URL : http://arxiv.org/pdf/mtrl-th/9607005

J. R. Kitchin, K. Reuter, and M. Scheffler, in oxygen atmospheres, Physical Review B, vol.10, issue.12, p.75437, 2008.
DOI : 10.1007/s00339-003-2433-9

G. Bester, B. Meyer, and M. Fähnle, electron theory and statistical mechanics, Physical Review B, vol.82, issue.21, p.14492, 1999.
DOI : 10.1103/PhysRevLett.82.948

E. Belin-ferré, Electronic structure of hexagonal, Journal of Physics: Condensed Matter, vol.9, issue.44, p.9585, 1997.
DOI : 10.1088/0953-8984/9/44/013

S. A. Villaseca, Complex Metallic Alloy, The Journal of Physical Chemistry C, vol.115, issue.30, p.14922, 2011.
DOI : 10.1021/jp203727h

URL : https://hal.archives-ouvertes.fr/hal-00974222

M. Mihalkovi?, H. Elhor, and J. B. Suck, Atomic dynamics in Al-rich Al-Co alloys near the composition of the decagonal quasicrystal, Physical Review B, vol.23, issue.207, p.214301, 2001.
DOI : 10.1107/S0365110X67002439

G. Trambly-delaissardì-ere, D. N. Manh, L. Magaud, J. P. Julien, F. Cyrot-lackmann et al., Electronic structure and hybridization effects in Hume-Rothery alloys containing transition elements, Physical Review B, vol.20, issue.11, p.7920, 1995.
DOI : 10.1051/jphysrad:01959002002-3016000

M. Oku, T. Shishido, H. Matsuta, and K. Wagatsuma, Comparison of the background corrected valence band XPS spectra of Fe and Co aluminides and silicides with their electronic structures, Journal of Electron Spectroscopy and Related Phenomena, vol.153, issue.3, p.75, 2006.
DOI : 10.1016/j.elspec.2006.06.006

F. U. Hillebrecht, J. C. Fuggle, P. A. Bennett, Z. Zolnierek, and C. , Electronic structure of Ni and Pd alloys. II. X-ray photoelectron core-level spectra, Physical Review B, vol.11, issue.4, p.2179, 1983.
DOI : 10.1088/0305-4608/11/8/024

M. Kraj?í and J. Hafner, Magnetism at surfaces and defects in icosahedral Al-Pd-Mn quasicrystals, Physical Review B, vol.58, issue.21, p.214419, 2009.
DOI : 10.1103/PhysRevB.76.024207

M. Gatti, Ab initio Calculations of Many-Body Effects in Electronic Spectra ( ´ Ecole Polytechnique, 2007.

J. Grin, U. Burkhardt, M. Ellner, and K. Peters, Crystal structure of orthorhombic Co4Al13, Journal of Alloys and Compounds, vol.206, issue.2, p.243, 1994.
DOI : 10.1016/0925-8388(94)90043-4

URL : https://hal.archives-ouvertes.fr/hal-00978014

H. Shin, studies, Physical Review B, vol.86, issue.8, p.85411, 2011.
DOI : 10.1103/PhysRevB.69.153404

URL : https://hal.archives-ouvertes.fr/hal-01157637

K. Kovnir, A new approach to well-defined, stable and site-isolated catalysts, Science and Technology of Advanced Materials, vol.2, issue.5, p.420, 2007.
DOI : 10.1021/jp036718t

M. Meier, J. Ledieu, M. Weerd, Y. Huang, G. J. Abreu et al., surface, Physical Review B, vol.87, issue.8, p.85414, 2015.
DOI : 10.1103/PhysRevB.84.085411

URL : https://hal.archives-ouvertes.fr/cea-00371815

S. Song and E. R. Ryba, Structural repeat units and repeat schemes for the Al-Cu-Co decagonal phase and its crystalline approximants, Philosophical Magazine Letters, vol.65, issue.2, p.85, 1992.
DOI : 10.1111/j.1365-2818.1987.tb01353.x

U. Burkhardt, M. Ellner, Y. Grin, and B. Baumgartner, Powder diffraction refinement of the Co2Al5 structure, Powder Diffraction, vol.64, issue.03, p.159, 1998.
DOI : 10.3891/acta.chem.scand.21-0647

A. Ormeci and Y. Grin, Chemical Bonding in Al5Co2: The Electron Localizability-Electron Density Approach, Israel Journal of Chemistry, vol.12, issue.11-12, p.1349, 2011.
DOI : 10.1016/j.intermet.2004.01.006

S. A. Villaseca, J. M. Dubois, and . Gaudry, complex metallic alloy, Philosophical Magazine, vol.13, issue.19-21, p.2894, 2011.
DOI : 10.1103/PhysRevLett.50.1998

URL : https://hal.archives-ouvertes.fr/hal-00974222

G. Kresse and J. Hafner, molecular dynamics for liquid metals, Physical Review B, vol.41, issue.1, p.558, 1993.
DOI : 10.1103/PhysRevB.41.1497

G. Kresse and J. Hafner, molecular-dynamics simulation of the liquid-metal???amorphous-semiconductor transition in germanium, Physical Review B, vol.48, issue.20, p.14251, 1994.
DOI : 10.1103/PhysRevB.48.13115

G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Computational Materials Science, vol.6, issue.1, p.15, 1996.
DOI : 10.1016/0927-0256(96)00008-0

G. Kresse and J. Furthmüller, total-energy calculations using a plane-wave basis set, Physical Review B, vol.2, issue.16, p.11169, 1996.
DOI : 10.1007/978-3-642-83058-7

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Physical Review Letters, vol.80, issue.18, p.3865, 1996.
DOI : 10.1063/1.446965

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)], Physical Review Letters, vol.78, issue.7, p.1396, 1997.
DOI : 10.1103/PhysRevLett.78.1396

K. Momma and F. Izumi, for three-dimensional visualization of crystal, volumetric and morphology data, Journal of Applied Crystallography, vol.51, issue.6, p.1272, 2011.
DOI : 10.1107/S0108767394013292

J. K. Nørskov, F. Studt, F. Abild-pedersen, and T. Bligaard, Fundamental Concepts in Heterogeneous Catalysis, 2014.
DOI : 10.1002/9781118892114

H. Ohtani, Al-Co Phase Diagram, ASM Alloy Phase Diagrams Database

B. Unal, C. J. Jenks, and P. A. Thiel, Comparison between experimental surface data and bulk structure models for quasicrystalline AlPdMn: Average atomic densities and chemical compositions, Physical Review B, vol.294, issue.296, p.195419, 2008.
DOI : 10.1016/j.susc.2005.02.012

L. Vitos, A. Ruban, H. Skriver, and J. Kollár, The surface energy of metals, Surface Science, vol.411, issue.1-2, p.186, 1998.
DOI : 10.1016/S0039-6028(98)00363-X

P. Le-modèle and . B?4co-est-Également-considéré, Basé sur le site A'3 mentionné précédemment, un second chemin réactionnel est proposé, comme indiqué sur la Fig. 4.4(bas) Pour simplifier les calculs et ne pas recalculer des énergies de dissociation de dihydrogène, on a supposé la présence d'hydrogène proche du site A'3 (la diffusion d'hydrogène en surface dispose d'une faible barrière). L'étape limitante constitue alors la formation d

. En-ce-qui-concerne-la-sélectivité, le second critère à étudier, nous avons calculé l'énergie d'activation de la formation d'éthyle (C 2 H 5 ) Nous avons envisagé différentes configurations afin de ne pas rater le chemin le plus probable énergétiquement (les configurations sont visibles sur la Fig

L. Sélectivité-est-calculée-d, après les différentes définitions données (section 1.11.3), en utilisant l'énergie d'activation la plus favorable (TS5 3 ) pour la formation d'éthyle, qui est de 60 kJ, mol ?1 . On obtient pour P B A4: [?59, ?27, pp.35-36

. Il-est-intéressant-de-noter and . Qu, aucun des deux chemins étudiés sur la surface Al 5 Co 2 (210) n'est sélectif, même en utilisant notre correction, c'est-à-dire en considérant l'influence d'un atome d'hydrogène sur la désorption de C 2 H 4 (?E select?3 )

P. Dans-le-cas-du-chemin and . A4, énergie d'activation de la déshydrogénation de l'éthyle en éthylène est faible (70 kJ.mol ?1 ) En combinant ce résultat avec l'importante énergie d'activation de la formation d'éthane (183 kJ.mol ?1 ), on peut conclure que l'éthyle déshydrogène en éthylène qui désorbe ensuite

D. Kandaskalov, J. Ledieu, V. Fournée, and É. Gaudry, (100) Surface toward Molecules Involved in the Semihydrogenation of Acetylene, The Journal of Physical Chemistry C, vol.118, issue.40, p.23032, 2014.
DOI : 10.1021/jp504906r

URL : https://hal.archives-ouvertes.fr/hal-01075982

F. Abild-pedersen, Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces, Physical Review Letters, vol.45, issue.1, p.16105, 2007.
DOI : 10.1016/0021-9517(90)90211-2

M. Kraj?í and J. Hafner, : Ga Enrichment Improves Selectivity, The Journal of Physical Chemistry C, vol.118, issue.23, p.12285, 2014.
DOI : 10.1021/jp5025075

M. Kraj?í and J. Hafner, Intermetallic Compound AlPd As a Selective Hydrogenation Catalyst: A DFT Study, The Journal of Physical Chemistry C, vol.116, issue.10, p.6307, 2012.
DOI : 10.1021/jp212317u

W. Dong and J. Hafner, dissociative adsorption on Pd(111), Physical Review B, vol.346, issue.300, p.15396, 1997.
DOI : 10.1016/0039-6028(95)00906-X

URL : https://hal.archives-ouvertes.fr/hal-00006615

D. Mei, P. A. Sheth, M. Neurock, and C. M. Smith, First-principles-based kinetic Monte Carlo simulation of the selective hydrogenation of acetylene over Pd(111), Journal of Catalysis, vol.242, issue.1, p.1, 2006.
DOI : 10.1016/j.jcat.2006.05.009

D. Mei, M. Neurock, and C. M. Smith, Hydrogenation of acetylene???ethylene mixtures over Pd and Pd???Ag alloys: First-principles-based kinetic Monte Carlo simulations, Journal of Catalysis, vol.268, issue.2, p.181, 2009.
DOI : 10.1016/j.jcat.2009.09.004

A. Borodzinski and G. C. Bond, Selective Hydrogenation of Ethyne in Ethene???Rich Streams on Palladium Catalysts. Part 1. Effect of Changes to the Catalyst During Reaction, Catalysis Reviews, vol.77, issue.2, p.91, 2006.
DOI : 10.1252/jcej.7.193

F. Studt, Identification of Non-Precious Metal Alloy Catalysts for Selective Hydrogenation of Acetylene, Science, vol.171, issue.2, p.1320, 2008.
DOI : 10.1016/S0166-9834(00)84168-8

F. Studt, On the Role of Surface Modifications of Palladium Catalysts in the Selective Hydrogenation of Acetylene, Angewandte Chemie International Edition, vol.113, issue.48, p.9299, 2008.
DOI : 10.1063/1.1323224

D. Zahn, F. Haarmann, and Y. Grin, Alloys: from Solid Solution to Phase Segregation, Zeitschrift f??r anorganische und allgemeine Chemie, vol.64, issue.14, p.2562, 2008.
DOI : 10.1080/14786443309462199

S. Zafeiratos, S. Piccinin, and D. Teschner, Alloys in catalysis: phase separation and surface segregation phenomena in response to the reactive environment, Catalysis Science & Technology, vol.77, issue.9, p.1787, 2012.
DOI : 10.1103/PhysRevB.77.155410

D. Kandaskalov, J. Ledieu, V. Fournée, and É. Gaudry, (100) Surface toward Molecules Involved in the Semihydrogenation of Acetylene, The Journal of Physical Chemistry C, vol.118, issue.40, p.23032, 2014.
DOI : 10.1021/jp504906r

URL : https://hal.archives-ouvertes.fr/hal-01075982

K. Kovnir, A new approach to well-defined, stable and site-isolated catalysts, Science and Technology of Advanced Materials, vol.2, issue.5, p.420, 2007.
DOI : 10.1021/jp036718t

U. Burkhardt, M. Ellner, Y. Grin, and B. Baumgartner, Powder diffraction refinement of the Co2Al5 structure, Powder Diffraction, vol.64, issue.03, p.159, 1998.
DOI : 10.3891/acta.chem.scand.21-0647

M. Meier, surface, Physical Review B, vol.87, issue.8, p.85414, 2015.
DOI : 10.1103/PhysRevB.84.085411

URL : https://hal.archives-ouvertes.fr/cea-00371815

A. Ormeci and Y. Grin, Chemical Bonding in Al5Co2: The Electron Localizability-Electron Density Approach, Israel Journal of Chemistry, vol.12, issue.11-12, p.1349, 2011.
DOI : 10.1016/j.intermet.2004.01.006

M. Armbrüster, R. Schlögl, and Y. Grin, Intermetallic compounds in heterogeneous catalysis???a quickly developing field, Science and Technology of Advanced Materials, vol.2007, issue.3, p.34803, 2014.
DOI : 10.1021/ja0742784

T. Jiang, Trends in CO Oxidation Rates for Metal Nanoparticles and Close-Packed, Stepped, and Kinked Surfaces, The Journal of Physical Chemistry C, vol.113, issue.24, p.10548, 2009.
DOI : 10.1021/jp811185g

G. Kresse and J. Hafner, molecular dynamics for liquid metals, Physical Review B, vol.41, issue.1, p.558, 1993.
DOI : 10.1103/PhysRevB.41.1497

G. Kresse and J. Hafner, molecular-dynamics simulation of the liquid-metal???amorphous-semiconductor transition in germanium, Physical Review B, vol.48, issue.20, p.14251, 1994.
DOI : 10.1103/PhysRevB.48.13115

G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Computational Materials Science, vol.6, issue.1, p.15, 1996.
DOI : 10.1016/0927-0256(96)00008-0

G. Kresse and J. Furthmüller, total-energy calculations using a plane-wave basis set, Physical Review B, vol.2, issue.16, p.11169, 1996.
DOI : 10.1007/978-3-642-83058-7

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Physical Review Letters, vol.80, issue.18, p.3865, 1996.
DOI : 10.1063/1.446965

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)], Physical Review Letters, vol.78, issue.7, p.1396, 1997.
DOI : 10.1103/PhysRevLett.78.1396

K. Momma and F. Izumi, for three-dimensional visualization of crystal, volumetric and morphology data, Journal of Applied Crystallography, vol.51, issue.6, p.1272, 2011.
DOI : 10.1107/S0108767394013292

G. Henkelman, B. P. Uberuaga, and H. Jónsson, A climbing image nudged elastic band method for finding saddle points and minimum energy paths, The Journal of Chemical Physics, vol.13, issue.22, p.9901, 2000.
DOI : 10.1103/PhysRevLett.85.618

G. Henkelman and H. Jónsson, Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points, The Journal of Chemical Physics, vol.82, issue.22, p.9978, 2000.
DOI : 10.1063/1.475306

S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction, Journal of Computational Chemistry, vol.10, issue.15, p.1787, 2006.
DOI : 10.1007/s002140050244

M. Kraj?í and J. Hafner, : Ga Enrichment Improves Selectivity, The Journal of Physical Chemistry C, vol.118, issue.23, p.12285, 2014.
DOI : 10.1021/jp5025075

L. A. Kibler, A. M. El-aziz, R. Hoyer, and D. M. Kolb, Tuning Reaction Rates by Lateral Strain in a Palladium Monolayer, Angewandte Chemie International Edition, vol.60, issue.14, p.2080, 2005.
DOI : 10.1524/zpch.217.10.1265.20490

T. Jiang, Trends in CO Oxidation Rates for Metal Nanoparticles and Close-Packed, Stepped, and Kinked Surfaces, The Journal of Physical Chemistry C, vol.113, issue.24, p.10548, 2009.
DOI : 10.1021/jp811185g

R. J. Maurer, V. Ruiz, and A. Tkatchenko, Many-body dispersion effects in the binding of adsorbates on metal surfaces, The Journal of Chemical Physics, vol.143, issue.10, p.102808, 2015.
DOI : 10.1103/PhysRevB.82.153412

F. Abild-pedersen, Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces, Physical Review Letters, vol.45, issue.1, p.16105, 2007.
DOI : 10.1016/0021-9517(90)90211-2

M. M. Montemore and J. W. Medlin, Scaling relations between adsorption energies for computational screening and design of catalysts, Catal. Sci. Technol., vol.136, issue.141, p.3748, 2014.
DOI : 10.1021/ja411973p

M. Kraj?í and J. Hafner, Intermetallic Compound AlPd As a Selective Hydrogenation Catalyst: A DFT Study, The Journal of Physical Chemistry C, vol.116, issue.10, p.6307, 2012.
DOI : 10.1021/jp212317u

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Physical Review Letters, vol.80, issue.18, p.3865, 1996.
DOI : 10.1063/1.446965

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)], Physical Review Letters, vol.78, issue.7, p.1396, 1997.
DOI : 10.1103/PhysRevLett.78.1396

J. Heyd, G. E. Scuseria, and M. Ernzerhof, Hybrid functionals based on a screened Coulomb potential, The Journal of Chemical Physics, vol.118, issue.18, p.8207, 2003.
DOI : 10.1063/1.477422

M. Meier, J. Ledieu, M. Weerd, V. Fournée, and É. Gaudry, and (100) surfaces: Influence of bonding strength and annealing temperature on surface terminations, Physical Review B, vol.64, issue.7, p.75412, 2016.
DOI : 10.1016/S0039-6028(98)00363-X

URL : https://hal.archives-ouvertes.fr/hal-01284776

M. Meier, J. Ledieu, M. Weerd, Y. Huang, G. J. Abreu et al., surface, Physical Review B, vol.87, issue.8, p.85414, 2015.
DOI : 10.1103/PhysRevB.84.085411

URL : https://hal.archives-ouvertes.fr/cea-00371815

M. Meier, J. Ledieu, M. De-weerd, V. Fournée, and É. Gaudry, Surfaces d'approximants de quasicristaux décagonaux: Al 13 Co 4 (100) et Al, p.8

É. Fournée and . Gaudry, Interplay between bulk atomic clusters and surface structure in complex intermetallic compounds: the case study of the Al 5 Co 2 (001) surface. M-SNOWS International Workshop on Nanomaterials, pp.8-11, 2014.

É. Fournée and . Gaudry, Interplay between bulk atomic clusters and surface structure in complex intermetallic compounds: the case study of the Al 5 Co 2 (001) surface, ECOSS 30 European Conference on Surface Science, 2014.

M. Meier, J. Ledieu, M. De-weerd, Y. Huang, G. J. Abreu et al., Influence of the 3-d cluster and preparation conditions on the Al 5 Co 2 (100) surface. C-MAC days, 2014.

M. Meier, J. Ledieu, É. Gaudry, M. De-weerd, and V. Fournée, Structural investigation of the (001) surface of Al 5 Co 2, AVS 60th International Symposium and Exhibition, Applied Surface Science Division award finals, 2013.

M. Meier, J. Ledieu, É. Gaudry, M. De-weerd, and V. Fournée, Structural investigation of the (001) surface of Al 5 Co 2, AVS 60th International Symposium and Exhibition, Quasicrystals and Complex Metal Alloys, 2013.

M. Meier, É. Gaudry, J. Ledieu, M. De-weerd, and V. Fournée, Structural investigation of the (001) surface of Al 5 Co 2 . C-MAC Days, pp.9-12, 2013.

M. Meier, É. Gaudry, J. Ledieu, M. De-weerd, and V. Fournée, Structural investigation of the (001) surface of Al 5 Co 2, Seminar EMMA, p.7, 2015.

. La-théorie-de-la-fonctionnelle-de-la-densité, Density Functional Theory", DFT en anglais) est présentée, ainsi que les approximations utilisées. Les paramètres liés à l'implémentation numérique sont également présentés et leurs précisions déterminées

. De-cobalt-dans-notre-cas, La fonctionnelle PBE-GGA est utilisée car elle est bien adaptée à notre travail qui comprend des calculs sur des systèmes massifs

. Puisque-les-potentiels, A.9 dépendent de ?( r), il faut résoudre cette équation de manière autocohérente . Les itérations auto-cohérentes sont détaillées dans Fig

. En-pratique, Vienna ab initio Simulation Package (VASP) [9] [10] [11] [12] [13] implémenté sur le cluster de l'IJL et sur le cluster de l'IDRIS (Institut du développement et des ressources en informatique scientifique [14]). L'implémentation numérique engendre des approximations supplémentaires, Phys. Rev, vol.136, p.864, 1964.

W. Kohn and L. J. Sham, Self-Consistent Equations Including Exchange and Correlation Effects, Physical Review, vol.119, issue.4A, p.1133, 1965.
DOI : 10.1103/PhysRev.119.1153

P. A. Dirac, Quantum Mechanics of Many-Electron Systems, Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, vol.123, issue.792, p.714, 1929.
DOI : 10.1098/rspa.1929.0094

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Physical Review Letters, vol.80, issue.18, p.3865, 1996.
DOI : 10.1063/1.446965

J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)], Physical Review Letters, vol.78, issue.7, p.1396, 1997.
DOI : 10.1103/PhysRevLett.78.1396

C. C. Roothaan, New Developments in Molecular Orbital Theory, Reviews of Modern Physics, vol.46, issue.2, p.69, 1951.
DOI : 10.1051/jcp/1949460497

]. S. Kurth, J. P. Perdew, and P. Blaha, Molecular and solid-state tests of density functional approximations: LSD, GGAs, and meta-GGAs, International Journal of Quantum Chemistry, vol.46, issue.4-5, p.889, 1999.
DOI : 10.1016/0370-2693(76)90519-0

G. Kresse and J. Hafner, molecular dynamics for liquid metals, Physical Review B, vol.41, issue.1, p.558, 1993.
DOI : 10.1103/PhysRevB.41.1497

G. Kresse and J. Hafner, molecular-dynamics simulation of the liquid-metal???amorphous-semiconductor transition in germanium, Physical Review B, vol.48, issue.20, p.14251, 1994.
DOI : 10.1103/PhysRevB.48.13115

G. Kresse and J. Furthmüller, total-energy calculations using a plane-wave basis set, Physical Review B, vol.2, issue.16, p.11169, 1996.
DOI : 10.1007/978-3-642-83058-7

G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Computational Materials Science, vol.6, issue.1, p.15, 1996.
DOI : 10.1016/0927-0256(96)00008-0

G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Physical Review B, vol.9, issue.3, p.1758, 1999.
DOI : 10.1103/PhysRevB.55.13479

P. E. Blochl, Projector augmented-wave method, Physical Review B, vol.44, issue.24, p.17953, 1994.
DOI : 10.1103/PhysRevB.44.13063

M. Hagen and M. W. Finnis, Point defects and chemical potentials in ordered alloys, Philosophical Magazine A, vol.11, issue.2, p.447, 1998.
DOI : 10.1016/1359-6454(96)00117-6

C. Colinet and J. Tedenac, First principles calculations in V???Si system. Defects in A15-V3Si phase, Computational Materials Science, vol.85, p.94, 2014.
DOI : 10.1016/j.commatsci.2013.12.044

URL : https://hal.archives-ouvertes.fr/hal-00997655

S. H. Vosko, L. Wilk, and M. Nusair, Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis, Canadian Journal of Physics, vol.58, issue.8, p.1200, 1980.
DOI : 10.1139/p80-159

E. Appendice and .. Scripts, 1 Liste des scripts/programmes en Python, p.159

E. Appendice, Scripts/programmes et logiciels Autres scripts utiles

K. Momma and F. Izumi, for three-dimensional visualization of crystal, volumetric and morphology data, Journal of Applied Crystallography, vol.51, issue.6, p.1272, 2011.
DOI : 10.1107/S0108767394013292