A multireference coupled-cluster study of electronic excitations in furan and pyrrole.
A multireference (MR), general-model-space (GMS), state-universal (SU), coupled-cluster (CC) method that considers singly (S) and doubly (D) excited cluster amplitudes relative to the reference configurations spanning the model space (GMS SU CCSD) is employed to investigate a number of low-lying excited states of two five-membered, six pi -electron aromatic ring molecules, namely, furan and pyrrole. An extended basis set that includes diffuse functions and molecule-centered Rydberg functions is employed. Computed vertical excitation energies are compared with experimental values as well as with other theoretical results, namely, those obtained by the equation-of-motion (EOM) CCSD method or, equivalently, the symmetry adapted cluster configuration interaction (SAC-CI) method, by the MR CI method, by MR perturbation theory, and by other methods whenever available. For excited states dominated by single-excitations the GMS SU CCSD energies represent an improvement relative to the most closely related EOM CCSD results by about 0.1 eV.
Li
Xiangzhu
X
Department of Applied Mathematics, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
Paldus
Josef
J
D003198:Computer Simulation; D004583:Electrons; D005663:Furans / Q000737:chemistry*; D011758:Pyrroles / Q000737:chemistry*; D011789:Quantum Theory
D005663:Furans; D011758:Pyrroles; C039281:furan