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

被引:63
作者
Hättig, C
Köhn, A
Hald, K
机构
[1] Forschungszentrum Karlsruhe, Inst Nanotechnol, D-76021 Karlsruhe, Germany
[2] Univ Karlsruhe, Inst Phys Chem, D-76128 Karlsruhe, Germany
[3] Aarhus Univ, Dept Chem, DK-8000 Aarhus, Denmark
关键词
D O I
10.1063/1.1457434
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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. (C) 2002 American Institute of Physics.
引用
收藏
页码:5401 / 5410
页数:10
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