화학공학소재연구정보센터
Journal of Chemical Physics, Vol.116, No.13, 5401-5410, 2002
First-order properties for triplet excited states in the approximated coupled cluster model CC2 using an explicitly spin coupled basis
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 pipi(*) 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 E-1(1u) states. It is found that the often used %T-1 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.