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Nll - C U n - 1) + E,An - 1)l = E d ( n ) - - E d ( n ) * . (6) Two different scaling laws have been proposed for ionisation potentials and electron affinities: a e2 E,(R) = Om + - 8R (7) 8-ae2 Fig. 9. Experimentally determined dissociation energies of mercury clusters ions (open circles) and calculated dissociation energies of neutral van der Waals clusters, scaled to the Hg, dissociation energy. the absolute energy scale of the dissociation energies, which is necessary since only ratios of dissociation energies are obtained from eqn (3).

Langosch, M. Oschwald and G. Tanner, J. Chem. , 1990,86,2473 4 K. Rademann, B. Kaiser, U. Even and F. Hensel, Phys. Rev. , 1987, 59,23 19. 5 C. Brkchignac, M. Broyer, Ph. Cauzac, G. Delacretaz, P. Labastie, J. P. Wolf and L. Woste, Phys. Rev. , 1988,60,275. C1usters 25 2473 J. CHEM. SOC. , 1990,86(13), 2473-2481 Experimental Study of the Transition from van der Waals, over Covalent to Metallic Bonding in Mercury Clusters Hellmut Haberland, Hans Kornmeler, Helge Langosch, Michael Oschwald and Gregor Tanner Fakultat fur Physik, Universitat Freiburg, Federal Republic of Germany The following properties have been measured for mercury clusters: (1) ionisation potentials of Hg, by electronimpact ionisation, (2)dissociation energies of Hg;, and (3) mass spectra for negatively charged mercury cluster ions (n 3 3).

As a function of pressure, temperature, concentration etc. e. the experimental observable depends smoothly on the experimental parameters in the transition region; an independent electron theory gives such a (Wilson) type of transition. If correlation between the electrons is strong, and an independent electron theory is therefore no longer valid, the smooth transition is replaced by an abrupt one, as emphasized repeatedly by M ~ t t and , ~ ~discussed below. Correlation treats that part of the electron-electron repulsion which has not been taken into account by a Hartree-Fock type of calculation.

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