Abstract
The aim of this lecture is to give an overlook about methods developed in infinite (bulk) and semi-infinite (surface) metallic materials and some tracks to extend them to finite size systems. In this framework we will first study the effect of bond breaking and dimension lowering on electronic structure, at surfaces of pure metals (surface states, atomic level shifts, reconstructions and relaxations) and in monometallic clusters. Then we will illustrate the influence of chemical ordering on electronic structure (and vice versa) by considering firstly bulk alloys (diagonal versus off-diagonal disorder) and then bimetallic surfaces (stress effect induced by either surface segregation or epitaxial growth). These two approaches will then naturally be combined in the peculiar case of nanoalloys. The methods will be developed following two main goals. The first one is to determine local electronic densities of states (LDOS), the knowledge of which is essential to the understanding and the analysis of nano-objects. The second one is to derive from these LDOS energetic models well suited to both the degree of complexity of the systems under study (bulk and surface crystalline structure, chemical ordering, …) and their implementation in numerical simulations (Molecular Dynamics, Monte Carlo). The different sections of the lecture will be illustrated by examples issued from studies performed on systems which can be considered as archetypal in the nano-alloy community, such as CoPt, CoAu and CuAg.
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References
Kohn, W., Becke, A.D., Parr, R.G.: Density functional theory of electronic structure. J. Phys. Chem. 100, 12974–12980 (1996) (and references therein)
Ashcroft, N.W.: The Fermi surface of aluminium. Philos. Mag. 8, 2055–2083 (1963)
Car, R., Parrinello, M.: Unified approach for molecular dynamics and density-functional theory. Phys. Rev. Lett. 55, 2471–2474 (1992)
Friedel, J.: Physics of Metals, vol. 1, Cambridge University Press, Cambridge (1978)
Ducastelle, F.: Structure électronique des métaux de transition et de leurs alliages. Thèse Orsay (1972)
Lambin, P., Gaspard, J.P.: Continued-fraction technique for tight-binding systems: a generalized-moments method. Phys. Rev. B 26, 4356–4368 (1982)
Haydock, R., Heine, V., Kelly, M.J.: Electronic structure based on local atomic environment for tight-binding bands. J. Phys. C 5, 2845–2858 (1972); C 8, 2591–2605 (1975)
Turchi, P., Ducastelle, F., Tréglia, G.: Band gaps and asymptotic behaviour of continued fraction coefficients. J. Phys. C 15, 2891–2924 (1982)
Jaafar, A., Goyhenex, C., Tréglia, G.: Role of sp-d hybridization in the formation of stacking defects at metal surfaces. Surf. Sci. 602, 2681–2688 (2008)
Ducastelle, F.: Order and Phase Stability in Alloys. North-Holland, Amsterdam (1991)
Turchi, P.: Structure électronique et stabilité des alliages de métaux de transition: effets de structure cristalline et d’ordre configurationnel. Thèse Paris (1984)
Desjonquères, M.C., Spanjaard D.: Concepts in Surface Physics. Springer, Berlin (1995)
Spanjaard, D., Guillot, C., Desjonquères, M.C., Tréglia, G., Lecante, J.: Surface core level spectroscopy of transition metals: a new tool for the determination of their surface structure. Surf. Sci. Rep. 5, 1–85 (1985)
Sawaya, S., Goniakowski, J., Mottet, C., Saúl, A., Tréglia, G.: Charge redistribution at Pd surfaces: ab initio grounds for tight-binding interatomic potentials. Phys. Rev. B 56, 12161–12166 (1997)
Jaafar, A., Goyhenex, C., Tréglia, G.: Rules for tight-binding calculations in bimetallic compounds based on density functional theory: the case of CoAu. J. Phys. Condens. Matter. 22, 505503 (2010)
Rosato, V., Guillopé, M., Legrand, B.: Thermodynamical and structural properties of fcc transition metals using a simple tight-binding model. Philos. Mag. A 59, 321–336 (1989)
Spanjaard, D., Desjonquères, M.C.: Universal features of bonding in metals. Phys. Rev. B 30, 4822–4827 (1984)
Foiles, S.M., Baskes, M.I., Daw, M.S.: Embedded atom method functions for the fcc metals Cu, Ag, Au, Ni, Pd, Pt and their alloys. Phys. Rev. B 33, 7983–7991 (1986)
Garofalo, M., Tosatti, E., Ercolessi, F.: Structure, energetics, and low temperature behaviour of the Au(110) reconstructed surface. Surf. Sci. 188, 321–326 (1987)
Guillopé, M., Legrand, B.: (110) surface stability in noble metals. Surf. Sci. 215, 577–595 (1989)
Legrand, B., Tréglia, G., Desjonquères, M.C., Spanjaard, D.: A “quenched molecular dynamics” approach to the atomic stability of the (100) face of bcc transition metals. J. Phys. C 19, 4463–4472 (1986)
Mottet,C.: Étude par simulation numérique d’agrégats libres mono- et bi-métalliques. Thèse, Université Aix-Marseille II (1997)
Mottet, C., Tréglia, G., Legrand, B.: Electronic structure of Pd clusters in the tight-binding approximation: influence of spd-hybridization. Surf. Sci. 352–354, 675–679 (1996)
Hammer, B., Morikawa, Y., Norskov, J.K.: CO Chemisorption at metal surfaces and overlayers. Phys. Rev. Lett. 76, 2141–2144 (1996)
Mottet, C., Tréglia, G., Legrand, B.: New magic numbers in metallic clusters: an unexpected metal dependence. Surf. Sci. 383, L719–L727 (1997)
Wang, L.L., Johnson, D.D.: Density functional study of structural trends for late-transition-metal 13-atom clusters. Phys. Rev. B 75, 235405 (2007)
Papaconstantopoulos, D.A.: Handbook of Electronic Structure of Elemental Solids. Plenum, New York (1986)
Velicky, B., Kirkpatrick, S., Ehrenreich, H.: Single-site approximations in the electronic theory of simple binary alloys. Phys. Rev. B 175, 747–766 (1968)
Bieber, A., Ducastelle, F., Gautier, F., Tréglia, G., Turchi, P.: Electronic structure and relative stabilities of L12 and DO22 ordered structures occurring in transition metal alloys. Solid State Comm. 45, 585–590 (1983)
Kudrnovsky, J., Bose, S.K., Andersen, O.K.: Comparative study of the electronic structure of ordered, partially ordered and disordered phases of the Cu3Au alloy. Phys. Rev. B 43, 4613–4621 (1991)
Olovsson, W., Göransson, C., Pourovski, L.V., Johansson, B., Abrikosov, I.A.: Core-level shifts in fcc random alloys: a first-principles approach. Phys. Rev. B 72, 064203 (2005)
Goyhenex, C., Tréglia, G.: Unified picture of d band and core level shifts in transition metal alloys. Phys. Rev. B 83, 075101 (2011)
Tréglia, G., Ducastelle, F., Gautier, F.: Generalised perturbation theory in disordered transition metal alloys: application to the self-consistent calculation of ordering energies. J. Phys. F 8, 1437–1456 (1978)
Lee, Y.-S., Lim, K.-Y., Chung, Y.-D., Wang, C.-N., Jeon, Y.: XPS core-level shifts and XANES studies of Cu-Pt and Co-Pt alloys. Surf. Interface Anal. 30, 475–478 (2000)
Bieber, A., Gautier, F., Tréglia, G., Ducastelle, F.: Electronic structure, pairwise interactions and ordering energies in binary fcc transition metal alloys. Solid State Comm. 39, 149–153 (1981)
Los, J., Mottet, C., Tréglia, G., Goyhenex, C.: Ordering trends in transition metal alloys from tight-binding electronic structure calculations. Phys. Rev. B 84, 180202(R) (2011)
Meunier, I., Tréglia, G., Legrand, B.: Surface-induced ordering in phase separation systems: Influence of concentration and orientation. Surf. Sci. 441, 225–239 (1999)
Tréglia, G., Legrand, B., Ducastelle, F.: Segregation and ordering at surfaces of transition metal alloys: the tight-binding ising model. Europhys. Lett. 7, 575–580 (1988)
Tréglia, G., Legrand, B.: Surface-sandwich segregation in PtNi and AgNi alloys: two different physical origins for the same phenomenon. Phys. Rev. B 35, 4338–4344 (1987)
Creuze, J., Braems, I., Berthier, F., Mottet, C., Tréglia, G., Legrand, B.: Model of surface segregation driving forces and their coupling. Phys. Rev. B 78, 075413 (2008)
Tréglia, G., Legrand, B., Ducastelle, F., Saúl, A., Gallis, C., Meunier, I., Mottet, C., Senhaji, A.: Alloy surfaces: Segregation, reconstruction and phase transitions. Comput. Mat. Sci. 15, 196–235 (1999)
Goyhenex, C.: Revised tight-binding second moment potential for transition metal surfaces. Surf. Sci. 606(3–4), 325–328 (2012)
Mottet, C., Tréglia, G., Legrand, B.: Theoretical investigation of chemical and morphological ordering in PdcCu1−c clusters. Phys. Rev. B 66, 045413 (2002)
Moreno, V., Creuze, J., Berthier, F., Mottet, C., Tréglia, G., Legrand, B.: Site segregation in size-mismatched nanoalloys: application to Cu–Ag. Surf. Sci. 600, 5011–5020 (2006)
Amara, H., Bichara, C., Ducastelle, F.: Understanding the nucleation mechanisms of carbon nanotubes in catalytic chemical vapor deposition. Phys. Rev. Lett. 100, 056105 (2008)
Los, J.H., Pellenq, J.M.: Determination of the bulk melting temperature of nickel using Monte Carlo simulations: inaccuracy of extrapolation from cluster melting temperatures. Phys. Rev. B 81, 064112 (2010)
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Tréglia, G., Goyhenex, C., Mottet, C., Legrand, C., Ducastelle, F. (2012). Electronic Structure of Nanoalloys: A Guide of Useful Concepts and Tools. In: Alloyeau, D., Mottet, C., Ricolleau, C. (eds) Nanoalloys. Engineering Materials. Springer, London. https://doi.org/10.1007/978-1-4471-4014-6_5
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