Metallic bonding due to correlations: A quantum chemical ab-initio calculation of the cohesive energy of mercury

摘要

Solid mercury in the rhombohedral structure is unbound within theself-consistent field (Hartree-Fock) approximation. The metallic binding isentirely due to electronic correlations. We determine the cohesive energy ofsolid mercury within an ab-initio many-body expansion for the correlation part.Electronic correlations in the $5d$ shell contribute about half to the cohesiveenergy. Relativistic effects are found to be very important. Very goodagreement with the experimental value is obtained.