Gauge invariant coupled cluster response theory

Thomas Bondo Pedersen and Henrik Koch
Department of Chemistry, University of Odense, DK-5230 Odense M, Denmark

Christof Hättig
Department of Chemistry, Århus University, DK-8000 Århus C, Denmark

J. Chem. Phys. 110, 6318-6327 (1999).
(Received 20 November 1998; accepted 6 Febraury 1999)

We introduce a time-dependent coupled cluster based Lagrangian that includes orbital rotation. This Lagrangian is shown to give gauge invariant response properties for one-electron operators in the limit of a complete one-electron basis. The pole structure of the linear response function is compatible with that of the exact response function and the notorious problem of unphysical second-order poles in the Brueckner coupled cluster response theory is not present in this model. The total energy of the model is identical to the coupled cluster model using optimized orbitals recently revived by Sherrill et al. [J. Chem. Phys. 109, 4171 (1998)]. The model provides a straightforward approach for calculating magnetic response properties in a gauge invariant manner using coupled cluster wave functions.

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