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Journal Article

An orbital-invariant and strictly size extensive post-Hartree-Fock correlation functional

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Kollmar, C., & Neese, F. (2011). An orbital-invariant and strictly size extensive post-Hartree-Fock correlation functional. The Journal of Chemical Physics, 135(8): 084102. doi:10.1063/1.3624567.

Cite as: https://hdl.handle.net/21.11116/0000-0007-FF5D-3
A strictly size extensive post-Hartree-Fock correlation functional being invariant with respect to orbital transformations within the occupied and virtual subspaces is presented. While avoiding the necessity to solve additional Z vector equations for the calculation of properties and energy gradients, this functional reproduces almost exactly the results of coupled-cluster singles doubles (CCSD) calculations. In particular, it is demonstrated that the method is rigorous in the sense that it can be systematically improved by the perturbative inclusion of triple excitations in the same way as CCSD. As to the computational cost, the presented approach is somewhat more expensive than the CCSD if the energy is variationally optimized with respect to both the orbitals and the excitation amplitudes. Replacement of orbital optimization by the Brueckner condition reduces the computational cost by a factor of two, thus making the method less expensive than CCSD.