100 years of physical chemistry by Royal Society of Chemistry (Great Britain)

By Royal Society of Chemistry (Great Britain)

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SOC. mass ion source selector e;hv ion refLecta 0 00 N free flight region van der Waals Fw Z Schematicdiagram of the apparatus. A continuous supersonic HgjAr expansion produces the clusters. They can be i o n i d by electron or photon impact. An electric pulse between the plates PO and Pi acdcrates ions into the time-of-flight mass spectrometer. The first time focus is at the slit of the mass sclector, the second is at the detector 11. ThC mass selector can be uscd to select one mass only, say HI&,which can subsequently decay in the free-flight region into Hg:p + H g due to internal excitation.

1990,86,2473. An enduring clichk in cluster science is the continuing quest to ‘bridge the gap’ between properties characteristic of individual atoms or molecules, and the behaviour of those same substances when in the condensed phase. The type of question a cluster scientist might wish to address would be along the line of: how many water molecules does it take to dissolve sodium chloride? or, how many metal atoms does it take to construct an electrical conductor? In practice it has often proved very difficult to realise the clichC at a molecular level; the length scale over which many physical properties operate is often too large to be investigated using small numbers of atomic or molecular building blocks, For example, the transition from icosahedral to octahedral geometry in solid argon requires -2000 atoms, and to match the melting temperature of bulk gold, clusters need to contain several million atoms.

If Hg were t o stay van der Waals bound in the bulk, its cohesive energy would be ca. 378 meV. 67 eV. The dashed line marked ‘mean metallic’ gives the averaged cohesive energies for the prototype metallic systems of N a and K, also scaled to the bulk cohesive energy of Hg. 16 The individual data points are not given, as they would confuse this figure. The cohesive energies of neutral N a and K clusters agree remarkably well with the classical spherical droplet model Two transformations are applied to the data of fig.

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