Higher excitations for an exponential multireference wavefunction Ansatz and single-reference based multireference coupled cluster Ansatz: application to model systems H(4), P(4), and BeH(2).
This article reports on the convergence of the exponential multireference wavefunction Ansatz (MRexpT) [J. Chem. Phys. 123, 84102 (2005)] and the single-reference based multireference coupled cluster Ansatz [J. Chem. Phys. 94, 1229 (1991)] with respect to higher cluster excitations. The approaches are applied to the H(4), P(4), and BeH(2) model systems according to the recently published analysis by Evangelista et al. [J. Chem. Phys. 125, 154113 (2006)]. The results show both MRexpT and SRMRCC to be highly accurate although SRMRCC shows problems due to its lack of Fermi vacuum invariance (symmetry breaking).
Hanrath
Michael
M
Institute for Theoretical Chemistry, University of Cologne, Cologne, Germany. michael.hanrath@uni-koeln.de