Self-consistent field method for open-shell systems within the density-matrix functional theory

The unrestricted Hartree-Fock method is extended to correlation calculation within the density-matrix functional theory. The method is derived from an entropic cumulant functional for the correlation energy. The eigenvalue equations for the spin-orbitals are modified by the orbital occupation numbers. The Euler equation for the occupation numbers results in the Fermi-Dirac distribution, which is very efficient to update as soon as the orbital eigenvalue equations are solved. The method is demonstrated on the ground state of O2$$ {}_2 $$.

Automated summary

This article extends the unrestricted Hartree-Fock method to correlation calculation within the density-matrix functional theory. The method is derived from an entropic cumulant functional for the correlation energy. The eigenvalue equations for the spin-orbitals are modified by the orbital occupation numbers. The method is demonstrated on the ground state of O2.