Implementation of RI-CC2 triplet excitation energies with an application to trans-azobenzene

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

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

Phys. Chem. Chem. Phys. 4, 2111-2118 (2002).
(Received 27th November 2001; accepted 4th February 2002)

Triplet excitation energies within the approximate coupled cluster singles and doubles model CC2 have been implemented using an explicitly spin coupled basis and the resolution of the identity approximation for two-electron integrals. This approach reduces substantially the requirements for CPU time, disk space and memory and extends the applicability of CC2 for triplet excited states to molecules that could not be studied before with this method. We report an application to the lowest singlet and triplet vertical excitation energies of trans-azobenzene. An accurate ab initio geometry optimized at the MP2/cc-pVTZ level is presented and CC2 calculations in the aug-cc-pVTZ basis set with 874 basis functions are combined with coupled cluster singles and doubles (CCSD) calculations in modest basis sets to obtain best possible estimates for the vertical excitation energies. The results show that recently reported SOPPA calculations are unreliable. Good agreement with experiment is obtained for the lowest excited singlet state S1, but for the lowest triplet state T1 the results indicate a large difference between the vertical excitation energy and the experimentally observed transition.

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