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The particular features of Cr 2 which make the description of the region near Re so difficult are i) that we are dealing with a quintuple bond and ii) that the 3d overlaps are smaller even near R e than would be the case for, say, Zp orbitals in a first row mole- cule. The result is that Cr Z is a molecule which requires a complex MCSCF zero order description involving very high orders of excitation with respect to a single configuration SCF reference. Z5 a). Here we allowed single and double excitations from o various subsets of the most important configurations in the CASSCF wavefunction.

Due to limitations in the CI expansion and the small basis used, their conclusions while interesting are somewhat tentative. A computationally very different approach due to Goodgame and Goddard [14] assumes that the missing correlation serves mainly to correct the location of the ionic atomic asymptotes. Those authors attempt to include these effects by empirical modification of the integrals to correct the atomic ionization potentials and electron affinities to agree with experiment. This method does lead to a reasonable potential curve for Cr 2 although the bond length is somewhat too short which suggests that this method over corrects to some extent.

The clusters are prepared by condensation of laser- vaporized metal atoms in the roughly 2 atm of helium carrier gas flowing over the metal target rod shown in the diagram of Figure 1. The cluster-laden helium carrier gas then flows down the reaction tube and freely expands out the exit end to form a supersonic beam. Direct photoionization with an F2 excimer laser is then used downstream to determine the nature of the metal clusters. As shown in the Figure, there are a set of four needles near the upstream end of the reaction tube, and these can be fed from anyone of the four independent pulsed valves.

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