A spin-complete version of the spin-flip approach to bond breaking: What is the impact of obtaining spin eigenfunctions?

Journal of Chemical Physics

Volumn 118, Issue 20, 2003, Pages 9084-9094

  Sears, John S ^a   Sherrill, C David ^a   Krylov, Anna I ^b  

^a GEORGIA INSTITUTE OF TECHNOLOGY   (United States)

^b UNIVERSITY OF SOUTHERN CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; EIGENVALUES AND EIGENFUNCTIONS; ELECTRON ENERGY LEVELS; MOLECULAR STRUCTURE;

EXCITATION ENERGY; SPIN EIGENFUNCTIONS; SPIN FLIP CONFIGURATION INTERACTION SINGLES APPROACH;

MOLECULAR DYNAMICS;

EID: 0037603291     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1568735     Document Type: Article

References (26)

1. J. R. Thomas, B. J. DeLeeuw, G. Vacek, T. D. Crawford, Y. Yamaguchi, and H. F. Schaefer, J. Chem. Phys. 99, 403 (1993).
2. T. Helgaker, J. Gauss, P. Jørgensen, and J. Olsen, J. Chem. Phys. 106, 6430 (1997).
3. D. Feller and K. A. Peterson, J. Chem. Phys. 108, 154 (1998).
4. R. J. Bartlett and J. F. Stanton, in Computational Chemistry, edited by K. B. Lipkowitz and D. B. Boyd (VCH, New York, 1994), Vol. 5, pp. 65-169.
5. B. O. Roos, P. R. Taylor, and P. E. M. Siegbahn, Chem. Phys. 48, 157 (1980).
6. K. Ruedenberg, M. Schmidt, M. Gilbert, and S. Elbert, Chem. Phys. 71, 41 (1982).
7. M. Schmidt and M. Gordon, Annu. Rev. Phys. Chem. 49, 233 (1998).
8. A. I. Krylov, C. D. Sherrill, E. F. C. Byrd, and M. Head-Gordon, J. Chem. Phys. 109, 10669 (1998).
9. A. I. Krylov, Chem. Phys. Lett. 338, 375 (2001).
10. A. I. Krylov, Chem. Phys. Lett. 350, 522 (2001).
11. A. I. Krylov and C. D. Sherrill, J. Chem. Phys. 116, 3194 (2002).
12. Y. Shao, M. Head-Gordon, and A. Krylov, J. Chem. Phys. 118, 4807 (2003).
13. A. I. Krylov, J. Chem. Phys. 113, 6052 (2000).
14. C. D. Sherrill and H. F. Schaefer, The Configuration Interaction Method: Advances in Highly Correlated Approaches, in Advances in Quantum Chemistry, Vol. 34, edited by P.-O. Löwdin (Academic, New York, 1999), pp. 143-269.
15. J. Olsen, B. O. Roos, P. Jørgensen, and H. J. Aa. Jensen, J. Chem. Phys. 89, 2185 (1988).
16. C. D. Sherrill and H. F. Schaefer, J. Phys. Chem. 100, 6069 (1996).
17. J. Stanton, J. Chem. Phys. 101, 8928 (1994).
18. 2 molecule, respectively. However, in case of two identical fragments in a symmetric configuration, the lowest triplet state cannot be described by a single Slater determinant using symmetry-adapted orbitals. Therefore, it is necessary to use a symmetry-broken Hartree-Fock wave function to describe localization in the case of symmetrically arranged, noninteracting equivalent fragments.
19. H. Koch, H. Jørgen Aa. Jensen, and P. Jørgensen, J. Chem. Phys. 93, 3345 (1990).
20. AB,AB block. The interpretation of these roots requires caution as described in footnote 22 of Ref. 17. For example, due to the truncated nature of the excitation operators, the EOM and CI models fail to describe situations when both fragments are excited with the same accuracy as the excitations on individual fragments. Due to similar considerations, Eq. (1) does note mean that for two noninteracting fragments, the total SF energy of the composite system equals the sum of total SF energy of individual fragments; rather, the total SF energy is equal to the sum of SF energy of fragment A and Hartree-Fock energy for the fragment B.
21. J. B. Foresman, M. Head-Gordon, J. A. Pople, and M. J. Frisch, J. Phys. Chem. 96, 135 (1992).
22. S. Huzinaga, J. Chem. Phys. 42, 1293 (1965).
23. T. H. Dunning, J. Chem. Phys. 53, 2823 (1970).
24. W. D. Laidig, P. Saxe, and R. J. Bartlett, J. Chem. Phys. 86, 887 (1987)
25. L. Salem and C. Rowland, Angew. Chem. Int. Ed. Engl. 11, 92 (1972).
26. L. Slipchenko and A. Krylov, J. Chem. Phys. 117, 4694 (2002).