Communications: Accurate description of atoms and molecules by natural orbital functional theory

Abstract

The spin-conserving density matrix functional theory is used to propose an improved natural orbital functional. The Piris reconstruction functional, PNOF, which is based on an explicit form of the two-particle cumulant λ (Δ,) satisfying necessary positivity conditions for the two-particle reduced density matrix, is used to reconstruct the latter. A new approach (3), as well as an extension of the known ΔαΒ to spin-uncompensated systems lead to PNOF3. The theory is applied to the calculation of the total energies of the first- and second-row atoms (H-Ne) and a number of selected small molecules. The energy differences between the ground state and the lowest-lying excited state with different spin for these atoms, and the atomization energies of the considered molecules are also presented. The obtained values agree remarkably well with their corresponding both CCSD(T, full) and experimental values. © 2010 American Institute of Physics.