First-order properties for triplet excited states in the approximated coupled cluster model CC2 using an explicitly spin coupled basis

Christof Hättig
Forschungszentrum Karlsruhe, Institute of Nanotechnology, P.O. Box 3640, D-76021 Karlsruhe, Germany

Andreas Köhn
Institut für Physikalische Chemie, Universität Karlsruhe, D-76128 Karlsruhe, Germany

Kasper Hald
Department of Chemistry, Århus University, DK-8000 Århus C, Denmark

J. Chem. Phys. 116, 5401-5410 (2002).
(Received 14 November 2001; accepted 15 Janunary 2002)

An implementation is reported for first-order properties of excited triplet states within the approximate coupled cluster model CC2 using an explicitly spin coupled basis for the triplet excitation manifold and the resolution of the identity (RI) approximation for the electron repulsion integrals. Results are presented for the change of the second moment of charge upon excitation in the ππ valence and n=3 Rydberg states of benzene. Employing large basis sets with up to 828 functions, we obtain results close to the CC2 basis set limit and are able to resolve an uncertainty in the assignment of the lowest 1E1u states. It is found that the often used %T1 measure for the single excitation contribution to excited states is not reliable for a comparison across different excitation operator manifolds. An alternative diagnostic is proposed which provides a unique measure for the single excitation contribution that is independent of the chosen representation of the excitation operator manifold.

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