Open-shell coupled-cluster theory

Jayatilaka, Dylan; Lee, Timothy J.
June 1993
Journal of Chemical Physics;6/15/1993, Vol. 98 Issue 12, p9734
Academic Journal
An efficient formulation of our recently proposed [Chem. Phys. Lett. 199, 211 (1992)] open-shell singles and doubles coupled-cluster (OCCSD) method is presented. This formulation is in terms of spatial orbital one- and two-electron integrals. Our new OCCSD method is based on ‘‘symmetric spin orbitals’’ and is thus symmetric (or antisymmetric) in the spin indices. It therefore contains about half the number of independent parameters in the coupled-cluster wave function compared to other open-shell CCSD methods. It is shown that the formulation presented here contains less than half the number of n6 steps (where n is the number of molecular orbitals) of other recently proposed open-shell CCSD methods. A new approach by which amplitudes in our method may be compared with amplitudes in a previous OCCSD method is examined.


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