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RESEARCH PRODUCT

The vertical spectrum of H2CO revisited: (SC)2-CI and CC calculations

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The vertical electronic spectrum of formaldehyde has been studied by means of (SC)2-MR-SDCI and CCLR methods. Two basis sets of atomic natural orbitals (ANOs) complemented with a one-centre series of Rydberg orbitals were used. The first was taken from the CASPT2 study by Merchan, M., and Roos, B. O., 1995, Theoret. Chim. Acta, 92, 221, and may be described as C,O[4s3pld]/H[2slp] with a lslpld Rydberg series centred in the charge centroid of the 2B2 state of the cation. The second was a larger basis set that may be described as C,O[6s5p3d2f]/H[4s3p2d] + 3s3p3d in the same centre. The (SC)2 dressing may be applied efficiently to an MR-SDCI method and comparison with the dressed CAS-SDCI is satisfactory, in spite of the remarkable reduction in the CI space dimension. The consistency of the (SC)2-MR-SDCI results was tested also against the CCLR and CASPT2 results using the same basis sets and against the CCLR results using Dunning's aug- and daug-cc-pVQZ basis sets. The 3A1(π → π ∗) state is correctly placed...