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CC calculations with restricted open-shell (ROHF) references:

The MP2 and all CC calculations for ROHF reference wavefunctions are done by first transforming to a semi-canonical orbital basis which are defined by the eigenvectors of the occupied/occupied and virtual/virtual blocks of the Fock matrices of alpha and beta spin. No spin restrictions are applied in the cluster equations. This approach is sometimes also denoted as ROHF-UCCSD.

Note that if a frozen-core approximation is used, the semicanonical orbitals depend on whether the block-diagonalization of the Fock matrices is done in space of all orbitals or only in the space of the correlated valence orbitals. The two approaches lead thus to slightly different energies, but none of two is more valid or more accurate than the other. The ricc2 program uses the former scheme with the block-diagonalization done in the space of all molecular orbitals. The same scheme is used e.g. in the CFOUR program suite, but other codes as e.g. the implementation in MOLPRO use a block-diagonalization restricted to the active valence space.


next up previous contents index
Next: Perturbative triples corrections: Up: Characteristics of the Implementation Previous: Explicitly-correlated CCSD(F12) methods:   Contents   Index
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