A functional of the one-body-reduced density matrix derived from the homogeneous electron gas: Performance for finite systems.
An approximation for the exchange-correlation energy of reduced-density-matrix-functional theory was recently derived from a study of the homogeneous electron gas [N. N. Lathiotakis, N. Helbig, and E. K. U. Gross, Phys. Rev. B 75, 195120 (2007)]. In the present work, we show how this approximation can be extended appropriately to finite systems, where the Wigner Seitz radius r(s), the parameter characterizing the constant density of the electron gas, needs to be replaced. We apply the functional to a variety of molecules at their equilibrium geometry and also discuss its performance at the dissociation limit. We demonstrate that, although originally derived from the uniform gas, the approximation performs remarkably well for finite systems.
Lathiotakis
N N
NN
Theoretical and Physical Chemistry Institute, NHRF, Vass. Constantinou 48, GR-11635 Athens, Greece. lathiot@eie.gr
Helbig
N
N
Zacarias
A
A
Gross
E K U
EK