Mixed-sector intermediate Hamiltonian Fock-space coupled cluster approach.
An alternative formulation of the intermediate Hamiltonian Fock-space coupled cluster scheme developed before is presented. The methodological and computational advantages of the new formulation include the possibility of using a model space with determinants belonging to different Fock-space sectors. This extends the scope of application of the multireference coupled cluster method, and makes possible the use of quasiclosed shells (e.g., p2, d4) as reference states. Representative applications are described, including electron affinities of group-14 atoms, ionization potentials of group-15 elements, and ionization potentials and excitation energies of silver and gold. Excellent agreement with experiment (a few hundredths of an electronvolt) is obtained, with significant improvement (by a factor of 5-10 for p3 states) over Fock-space coupled cluster results. Many states not reachable by the Fock-space approach can now be studied.
Landau
Arie
A
School of Chemistry, Tel Aviv University, 69978 Tel Aviv, Israel.
Eliav
Ephraim
E
Ishikawa
Yasuyuki
Y
Kaldor
Uzi
U