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

TL;DR

This paper investigates the metallic bonding in solid mercury, revealing that electronic correlations and relativistic effects are crucial for accurately calculating its cohesive energy, with results closely matching experimental data.

Contribution

It provides an ab-initio many-body calculation of mercury's cohesive energy highlighting the importance of correlations and relativistic effects.

Findings

Electronic correlations contribute about half to the cohesive energy.

Relativistic effects are essential for accurate calculations.

Results agree well with experimental measurements.

Abstract

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