Orbital-optimized coupled-cluster theory does not reproduce the full configuration-interaction limit

Journal of Chemical Physics

Volumn 122, Issue 8, 2005, Pages

  Köhn, Andreas ^a   Olsen, Jeppe ^a  

^a AARHUS UNIVERSITY   (Denmark)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVE SPACE MODELS; CLUSTERS; ORBITAL GRADIENTS; ORBITAL ROTATIONS;

APPROXIMATION THEORY; FAILURE ANALYSIS; MATHEMATICAL MODELS; OPTIMIZATION;

MOLECULAR PHYSICS;

EID: 22944481843     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1850918     Document Type: Article

References (26)

1. C. D. Sherrill, A. I. Krylov, E. F. C. Byrd, and M. Head-Gordon, J. Chem. Phys. 109, 4171 (1998).
2. G. D. Purvis and R. J. Bartlett, J. Chem. Phys. 76, 1910 (1982).
3. G. E. Scuseria and H. F. Schaefer, Chem. Phys. Lett. 142, 354 (1987).
4. R. A. Chiles and C. E. Dykstra, J. Chem. Phys. 74, 4544 (1981).
5. N. C. Handy, J. A. Pople, M. Head-Gordon, K. Raghavachari, and G. W. Trucks, Chem. Phys. Lett. 164, 185 (1989).
6. J. Olsen, B. Roos, P. Jørgensen, and H. A. J. Jensen, J. Chem. Phys. 89, 2185 (1988).
7. A. I. Krylov, C. D. Sherrill, E. F. C. Byrd, and M. Head-Gordon, J. Chem. Phys. 109, 10669 (1998).
8. T. B. Pedersen, H. Koch, and C. Hättig, J. Chem. Phys. 110, 8318 (1999).
9. T. B. Pedersen, B. Fernández, and H. Koch, J. Chem. Phys. 114, 6983 (2001).
10. F. Aiga, K. Sasagane, and R. Itoh, Int. J. Quantum Chem. 51, 87 (1994).
11. J. Olsen and A. Köhn, LUCIA -a configuration interaction and coupled cluster program, University of Aarhus, 2004.
12. R.J. Bartlett, in Coupled-Cluster Theory: An Overview of Recent Developments, Modern Electronic Structure Theory Vol. 2, edited by, D. R. Yarkony, (World Scientific, Singapore, 1995), Chap. 16, pp. 1047-1131.
13. T. Helgaker, P. Jørgensen, and J. Olsen, Molecular Electronic-Structure Theory (Wiley, New York, 2000).
14. H. Koch, O. Christiansen, R. Kobayashi, P. Jørgensen, and T. Helgaker, Chem. Phys. Lett. 228, 233 (1994).
15. 1. This is, however, neither theoretically nor practically appealing as it leads to a highly redundant parametrization and both our and previous experience (Ref. 3) shows that convergence can hardly be obtained.
16. J. S. Arponen, Ann. Phys. (N.Y.) 151, 311 (1983).
17. J. S. Arponen, R. Bishop, and E. Pajanne, Phys. Rev. A 36, 2519 (1987).
18. T. Van Voorhis and M. Head-Gordon, Chem. Phys. Lett. 330, 585 (2000).
19. J. Olsen, J. Chem. Phys. 113, 7140 (2000).
20. N. Oliphant and L. Adamowicz, J. Chem. Phys. 94, 1229 (1991).
21. N. Oliphant and L. Adamowicz, J. Chem. Phys. 96, 3739 (1992).
22. M. Kállay, P. G. Szalay, and P. R. Surján, J. Chem. Phys. 117, 980 (2002).
23. High-spin open-shell systems may be treated using different definitions of subspaces for α - and β -spin orbitals. A generalized extension to open shells requires the definition of valence spaces which, however, need a true multireference coupled-cluster treatment.
24. The NOCC approach of Pedersen et al., Ref. 9, was not explicitly considered in the numerical section, but as the orbitals are variationally optimized and NOCC offers a larger variational manifold, we can expect the total energy to be equal to or lower than the OCC energy, i. e., NOCC will in neither case improve on OCC.
25. T. H. Dunning, J. Chem. Phys. 90, 1007 (1989);
26. D. E. Woon T. H. Dunning, J. Chem. Phys. 103, 4572 (1995).