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Comparison of coupled-cluster methods which include the effects of connected triple excitations

J. Chem. Phys. 93, 5851 (1990); doi:10.1063/1.459684

Issue Date: 15 October 1990

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Gustavo E. Scuseria
Department of Chemistry and Rice Quantum Institute, Rice University, Houston, Texas 77251-1892

Timothy J. Lee
NASA Ames Research Center, Moffett Field, California 94035
Electron correlation energies have been determined for 14 different molecules which represent a range of chemical bonding situations. These have been determined with the coupled-cluster single, double, and triple (CCSDT) excitation model as well as with several coupled-cluster methods that include only an approximate treatment of connected triple excitations, viz. CCSDT-1a, CCSDT-1b, CCSDT-2, CCSDT-3, CCSDT-4, and the recently proposed CCSD(T) method. All of the CCSDT-x methods include the effects of connected triple excitations in an iterative manner, whereas in CCSDT(T) these are included perturbationally. For chemical systems which are well represented by a single-determinant reference function, some of the CCSDT-x<s>methods (CCSDT-1a, CCSDT-1b, and CCSDT-4) perform marginally better than the CCSD(T) approach in reproducing the CCSDT results. However, as nondynamical correlation becomes more important the good agreement from the CCSDT-x methods deteriorates rapidly, while the error in CCSD(T) remains more consistent. For the 14 molecules considered in this work, the average error of the CCSD(T) method relative to CCSDT (667 µhartrees) is considerably below that obtained from any of the CCSDT-x methods. It is concluded that CCSD(T) is to be preferred over any of the other approximate methods, both because it is the least expensive and also because it is generally the most accurate approximation to CCSDT. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 31 May 1990; accepted 17 July 1990
Permalink: http://link.aip.org/link/?JCPSA6/93/5851/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.20.Tz
    Electronic structure of atoms and molecules: theory Specific calculations and results Electron correlation and CI calculations
  • YEAR: 1990

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (45)
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  1. J. Cižek, J. Chem. Phys. 45, 4256 (1966);
    2. Adv. Chem. Phys. 14, 35 (1969).
  2. S. A. Kucharski and R. J. Bartlett, Adv. Quantum Chem. 18, 281 (1986).
  3. R. J. Bartlett, J. Phys. Chem. 93, 1697 (1989).
  4. J. Noga and R. J. Bartlett, J. Chem. Phys. 86, 7041 (1987).
  5. R. J. Harrison and N. C. Handy, Chem. Phys. Lett. 95, 386 (1983).
  6. C. W. Bauschlicher and P. R. Taylor, J. Chem. Phys. 85, 2779 (1986).
  7. C. W. Bauschlicher, S. R. Langhoff, P. R. Taylor, and H. Partridge, Chem. Phys. Lett. 126, 436 (1986).
  8. Y. S. Lee, S. A. Kucharski, and R. J. Bartlett, J. Chem. Phys. 81, 5906 (1984).
  9. M. Urban, J. Noga, S. J. Cole, and R. J. Bartlett, J. Chem. Phys. 83, 4041 (1985).
  10. G. E. Scuseria and H. F. Schaefer, Chem. Phys. Lett. 152, 382 (1988).
  11. T. J. Lee, R. B. Remington, Y. Yamaguchi, and H. F. Schaefer, J. Chem. Phys. 89, 408 (1988).
  12. G. E. Scuseria, T. P. Hamilton, and H. F. Schaefer, J. Chem. Phys. 92, 568 (1990).
  13. C. W. Bauschlicher, S. R. Langhoff, and P. R. Taylor, Adv. Chem. Phys. (to be published).
  14. P. J. Knowles and N. C. Handy, Chem. Phys. Lett. 111, 315 (1984).
  15. S. M. Adler-Golden, S. R. Langhoff, C. W. Bauschlicher, and G. D. Carney, J. Chem. Phys. 83, 255 (1985).
  16. Y. Yamaguchi, M. J. Frisch, T. J. Lee, H. F. Schaefer, and J. S. Binkley, Theor. Chim. Acta. 69, 337 (1986).
  17. T. J. Lee, W. D. Allen, and H. F. Schaefer, J. Chem. Phys. 87, 7062 (1987).
  18. J. F. Stanton, W. N. Lipscomb, D. H. Magers, and R. J. Bartlett, J. Chem. Phys. 90, 1077 (1989).
  19. G. E. Scuseria, T. J. Lee, A. C. Scheiner, and H. F. Schaefer, J. Chem. Phys. 90, 5635 (1989).
  20. D. H. Magers, W. N. Lipscomb, R. J. Bartlett, and J. F. Stanton, J. Chem. Phys. 91, 1945 (1989).
  21. K. Raghavachari, G. W. Trucks, J. A. Pople, and E. Replogle, Chem. Phys. Lett. 158, 207 (1989).
  22. T. J. Lee and G. E. Scuseria, J. Chem. Phys. 93, 489 (1990).
  23. J. A. Pople, M. Head-Gordon, and K. Raghavachari, J. Chem. Phys. 87, 5968 (1987).
  24. G. E. Scuseria and H. F. Schaefer, J. Chem. Phys. 90, 3700 (1989).
  25. J. Paldus, J. Cizek, and B. Jeziorski, J. Chem. Phys. 90, 4356 (1989).
  26. T. J. Lee, A. P. Rendell, and P. R. Taylor, J. Phys. Chem. 94, 5463 (1990).
  27. K. Raghavachari, G. W. Trucks, J. A. Pople, and M. Head-Gordon, Chem. Phys. Lett. 157, 479 (1989).
  28. J. Almlöf and P. R. Taylor, J. Chem. Phys. 86, 4070 (1986).
  29. S. Huzinaga, J. Chem. Phys. 42, 1293 (1965).
  30. T. H. Dunning, J. Chem. Phys. 53, 2823 (1970).
  31. T. H. Dunning and P. J. Hay, Modern Theoretical Chemistry, edited by H. F. Schaefer (Plenum, New York, 1977), Vol. 4, pp. 1–27.
  32. T. J. Lee and H. F. Schaefer, J. Chem. Phys. 83, 1784 (1985).
  33. T. H. Dunning, J. Chem. Phys. 55, 716 (1971).
  34. F. B. van Duijneveldt, IBM Research Report RJ 945 (1971).
  35. T. J. Lee, J. Am. Chem. Soc. 111, 7362 (1989).
  36. C. W. Bauschlicher, S. R. Langhoff, H. Partridge, and L. A. Barnes, J. Chem. Phys. 91, 2399 (1989).
  37. Q. E. Scuseria, C. L. Janssen, and H. F. Schaefer, J. Chem. Phys. 89, 7382 (1988).
  38. G. E. Scuseria and H. F. Schaefer, Chem. Phys. Lett. 146, 23 (1988).
  39. MOLECULE-SWEDEN is an electronic structure program system written by J. Almlöf, C. W. Bauschlicher, M. R. A. Blomberg, D. P. Chong, A. Heiberg, S. R. Langhoff, P. Malmqvist, A. P. Rendell, B. O. Roos, P. E. M. Siegbahn, and P. R. Taylor.
  40. T. J. Lee and J. E. Rice, Chem. Phys. Lett. 150, 406 (1988).
  41. T. J. Lee and P. R. Taylor, Int. J. Quantum Chem. Symp. 23, 199 (1989).
  42. T. J. Lee, J. E. Rice, G. E. Scuseria, and H. F. Schaefer, Theor. Chim. Acta 75, 81 (1989).
  43. The CCSDT total energy is −75.747 060 EH with r = 2.4 a0. The molecular orbitals were taken from the 3Piu state as discussed in Ref. 44.
  44. C. W. Bauschlicher and S. R. Langhoff, J. Chem. Phys. 87, 2919 (1987).
  45. A. P. Rendell, T. J. Lee, and P. R. Taylor, J. Chem. Phys. 92, 7050 (1990).

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