Comptes Rendus
no. 3
Agrégats comme précurseurs des nano-objets/Clusters as precursors of nano-objects
Structure of nano-objects through polarizability and dipole measurements
[Structure des nano-objets determinée par mesures de polarisabilité et de dipôle]
Michel Broyer1 ; Rodolphe Antoine1 ; Emmanuel Benichou1 ; Isabelle Compagnon1 ; Philippe Dugourd1 ; Driss Rayane1
1 Laboratoire de spectrométrie ionique et moléculaire UMR n 5579, CNRS et université Claude Bernard, Lyon I, bâtiment Alfred Kastler, 43, boulevard du 11 Novembre 1918, 69622 Villeurbanne cedex, France
Comptes Rendus. Physique, Volume 3 (2002) no. 3, pp. 301-317.

La polarisabilité statique et le dipôle électrique permanent sont des quantités importantes pour comprendre les propriétés électroniques et structurales d'un agrégat. Dans cet article nous présentons les différents montages expérimentaux utilisés pour ces mesures et les simulations nécessaires à l'interprétation des résultats. Les cas des agrégats polaires et non polaires sont distingués et l'influence de la rigidité de l'agrégat sur son mouvement dans un champ électrique est discutée. Ces deux premières parties sont suivies par une revue des mesures réalisées sur des agrégats atomiques et des agrégats mixtes. Pour les agrégats atomiques, la polarisabilité est reliée à la nature de la liaison. Dans les métaux simples comme les agrégats alcalins, les résultats sont bien expliqués par la délocalisation des électrons de valence, caractéristique de la liaison métallique. Pour les autres métaux, la polarisabilité reflète la difficulté à décrire simplement les propriétés électroniques de ces agrégats. Dans le cas de l'aluminium, les mesures de polarisabilité mettent en évidence une transition non-métal–métal avec l'augmentation de la taille de l'agrégat. Dans le cas du nickel, de fortes variations avec la taille sont observées, certainement dues à un fort couplage entre propriétés électroniques et structure atomique. L'évolution avec la taille pour les agrégats semi-conducteurs (silicium, germanium) et covalents (fullerènes) est différente de celle observée pour les agrégats métalliques. Les mesures réalisées sur les fullerènes illustrent l'influence prépondérante de la géométrie sur la valeur de la polarisabilité. Dans le cas des agrégats mixtes, le dipôle électrique est la mesure la plus simple de la densité de charge dans l'agrégat. Ce dipôle dépend des transferts de charge et de l'arrangement géométrique des atomes dans la particule. Les mesures de dipôle électrique permanent sont illustrées par les résultats obtenus récemment sur deux exemples très différents : les agrégats mixtes métal-fullerène où un fort transfert de charge se produit et les agrégats d'halogénure d'alcalin dominés par une structure ionique.

The electric polarizability and the electric permanent dipole are important quantities for understanding the electronic properties of a cluster. Experimental techniques, the simulations necessary to interpret the experimental results, and a review of measurements on atomic and mixed clusters are presented. For atomic clusters, the polarizability is related to the type of bonding. In simple metal clusters such as alkali clusters, the results are well interpreted by the electron delocalization characteristic of the metallic bonding. In other metal clusters, the polarizability reflects the difficulty of establishing a clear and regular picture of the size evolution of electronic properties. The size evolution observed for covalent and semiconductor clusters is different from the evolution for metal clusters, and the influence of the geometry is preponderant, as demonstrated in the case of fullerenes. For mixed clusters, the measurements of the electric dipole allows one to deduce the charge transfers and the geometric arrangement. This is illustrated in the case of the metal-fullerene system and alkali halide clusters.

Reçu le :
Accepté le :
Publié le :
DOI : 10.1016/S1631-0705(02)01318-X
Keywords: cluster, electric polarizability, electric permanent dipole, metal-fullerene system, alkali halide cluster
Mots-clés : agrégat, polarisabilité statique, dipôle électrique permanent, métal-fullerène, agrégats d'halogénure d'alcalin

Michel Broyer 1 ; Rodolphe Antoine 1 ; Emmanuel Benichou 1 ; Isabelle Compagnon 1 ; Philippe Dugourd 1 ; Driss Rayane 1

1 Laboratoire de spectrométrie ionique et moléculaire UMR n 5579, CNRS et université Claude Bernard, Lyon I, bâtiment Alfred Kastler, 43, boulevard du 11 Novembre 1918, 69622 Villeurbanne cedex, France 
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Michel Broyer; Rodolphe Antoine; Emmanuel Benichou; Isabelle Compagnon; Philippe Dugourd; Driss Rayane. Structure of nano-objects through polarizability and dipole measurements. Comptes Rendus. Physique, Volume 3 (2002) no. 3, pp. 301-317. doi : 10.1016/S1631-0705(02)01318-X. https://comptes-rendus.academie-sciences.fr/physique/articles/10.1016/S1631-0705(02)01318-X/

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  • R. Antoine; M. Abd El Rahim; M. Broyer; D. Rayane; Ph. Dugourd Asymmetric Top Rotors in Electric Fields. II. Influence of Internal Torsions in Molecular Beam Deflection Experiments, The Journal of Physical Chemistry A, Volume 110 (2006) no. 33, p. 10006 | DOI:10.1021/jp0614345
  • V. S. Demidenko; N. L. Zaitsev; I. A. Nechaev; A. V. Nyavro; T. V. Men’shchikova; L. F. Skorentsev Changes in the electronic structure and energy of nanoclusters of 3d metals and TiFe and TiNi compounds upon BCC-HCP transformations, The Physics of Metals and Metallography, Volume 101 (2006) no. 2, p. 124 | DOI:10.1134/s0031918x06020050
  • P. Poulain; R. Antoine; M. Broyer; P. Dugourd Monte Carlo simulations of flexible molecules in a static electric field: electric dipole and conformation, Chemical Physics Letters, Volume 401 (2005) no. 1-3, p. 1 | DOI:10.1016/j.cplett.2004.11.025
  • M. Aubert-Frécon; F. Rabilloud; A.R. Allouche; D. Rayane; R. Antoine; M. Broyer; Ph. Dugourd Existence of weakly bound states for metal–benzene molecules confirmed from a long-range model, Chemical Physics Letters, Volume 405 (2005) no. 4-6, p. 422 | DOI:10.1016/j.cplett.2005.02.071
  • V. S. Demidenko; N. L. Zaitsev; A. V. Nyavro; T. V. Menshchikova Electronic structure and energy ratios of Ni3Al clusters in TiNi nanoparticles with an impurity Al atom, Russian Physics Journal, Volume 48 (2005) no. 10, p. 1073 | DOI:10.1007/s11182-006-0027-7
  • M. Abd El Rahim; R. Antoine; L. Arnaud; M. Broyer; D. Rayane; A. Viard; Ph. Dugourd Time-of-flight mass spectrometer coupled to a position sensitive detection, The European Physical Journal D, Volume 34 (2005) no. 1-3, p. 15 | DOI:10.1140/epjd/e2005-00101-2
  • S. N. Shore; R. D. Gehrz Photo-ionization induced rapid grain growth in novae, Astronomy Astrophysics, Volume 417 (2004) no. 2, p. 695 | DOI:10.1051/0004-6361:20034243
  • M. Abd El Rahim; R. Antoine; L. Arnaud; M. Barbaire; M. Broyer; Ch. Clavier; I. Compagnon; Ph. Dugourd; J. Maurelli; D. Rayane Position sensitive detection coupled to high-resolution time-of-flight mass spectrometry: Imaging for molecular beam deflection experiments, Review of Scientific Instruments, Volume 75 (2004) no. 12, p. 5221 | DOI:10.1063/1.1813112
  • Michael Filatov; Dieter Cremer Calculation of electric properties using regular approximations to relativistic effects: The polarizabilities of RuO4, OsO4, and HsO4 (Z=108), The Journal of Chemical Physics, Volume 119 (2003) no. 3, p. 1412 | DOI:10.1063/1.1580473
  • Isabelle Compagnon; Rodolphe Antoine; Driss Rayane; Michel Broyer; Philippe Dugourd Permanent Electric Dipole of Gas-Phase p-Amino Benzoic Acid, The Journal of Physical Chemistry A, Volume 107 (2003) no. 17, p. 3036 | DOI:10.1021/jp022247j

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