TY - JOUR
T1 - Open shells in reduced-density-matrix-functional theory
AU - Lathiotakis, N. N.
AU - Helbig, N.
AU - Gross, E. K.U.
PY - 2005/9
Y1 - 2005/9
N2 - Reduced-density-matrix-functional theory is applied to open-shell systems. We introduce a spin-restricted formulation by appropriately expressing approximate correlation-energy functionals in terms of spin-dependent occupation numbers and spin-independent natural orbitals. We demonstrate that the additional constraint of total-spin conservation is indispensable for the proper treatment of open-shell systems. The formalism is applied to the first-row open-shell atoms. The obtained ground-state energies are in very good agreement with the exact values as well as other state of the art quantum chemistry calculations.
AB - Reduced-density-matrix-functional theory is applied to open-shell systems. We introduce a spin-restricted formulation by appropriately expressing approximate correlation-energy functionals in terms of spin-dependent occupation numbers and spin-independent natural orbitals. We demonstrate that the additional constraint of total-spin conservation is indispensable for the proper treatment of open-shell systems. The formalism is applied to the first-row open-shell atoms. The obtained ground-state energies are in very good agreement with the exact values as well as other state of the art quantum chemistry calculations.
UR - http://www.scopus.com/inward/record.url?scp=28844454611&partnerID=8YFLogxK
U2 - 10.1103/PhysRevA.72.030501
DO - 10.1103/PhysRevA.72.030501
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AN - SCOPUS:28844454611
SN - 1050-2947
VL - 72
JO - Physical Review A - Atomic, Molecular, and Optical Physics
JF - Physical Review A - Atomic, Molecular, and Optical Physics
IS - 3
M1 - 030501
ER -