The convergence of the ab-initio many-body expansion for the cohesive energy of solid mercury

Abstract

A many-body expansion for mercury clusters of the form E = \sum_{i<j}Δε_{ij} + \sum_{i<j<k}Δε_{ijk} + ... \quad, does not converge smoothly with increasing cluster size towards the solid state. Even for smaller cluster sizes (up to n=6), where van der Waals forces still dominate, one observes bad convergence behaviour. For solid mercury the convergence of the many-body expansion can dramatically be improved by an incremental procedure within an embedded cluster approach. Here one adds the coupled cluster many-body electron correlation contributions of the embedded cluster to the bulk HF energy. In this way we obtain a cohesive energy (not corrected for zero-point vibration) of 0.79 eV in perfect agreement with the experimental value.

10 pages, 3 figures, accepted PRB

References in corpus (3)

• Cohesive energies of cubic III-V semiconductors
• Correlation effects in ionic crystals: I. The cohesive energy of MgO
• Metallic bonding due to correlations: A quantum chemical ab-initio calculation of the cohesive energy of mercury

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