Electronic structure of liquid mercury

Abstract

The electronic structure of liquid mercury is calculated using the scalar-relativistic tight-binding linear muffin-tin orbitals (TB-LMTO) basis and the recursion method. Calculations are performed for 1372 atom structural models of liquid mercury in the temperature range 150-250 °C, generated via the Metropolis Monte Carlo method and suitable two-body potentials. The existence of a pseudo-gap in the density of states (DOS), as conjectured by Mott, is carefully examined. The calculation produces a lowering of the DOS at the Fermi level with respect to the free electron value. The Mott g-factor is about 70%. The reason for the lowering of the DOS at the Fermi level below the free electron value is the hybridization of the narrow d band with the much broader sp band. This opens the so-called Fano gap in the sp density of states, pushing states from the middle of the sp band to the edges. However, the overall (sp+d) density of states has no deep or pronounced local minimum at the Fermi energy. For comparison, as well as a better understanding of the liquid state electronic structure, the DOS of Hg in various assumed crystalline phases is studied via the scalar-relativistic LMTO-ASA (atomic sphere approximation) method. We also present resistivity results for the temperature range 150-250 °C, calculated by using the Kubo-Greenwood formula and the TB-LMTO-recursion scheme.