A simple scheme for the direct calculation of ionization potentials with coupled-cluster theory that exploits established excitation energy methods

Journal of Chemical Physics

Volumn 111, Issue 19, 1999, Pages 8785-8788

  Stanton, John F ^a   Gauss, Jürgen ^b  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

^b JOHANNES GUTENBERG UNIVERSITY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000769983     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.479673     Document Type: Article

References (40)

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12. H. Koch, H. J. Aa. Jensen, T. Helgaker, and P. Jørgensen, J. Chem. Phys. 93, 3345 (1990); J. F. Stanton and R. J. Bartlett, ibid. 98, 7029 (1993); D. C. Comeau and R. J. Bartlett, Chem. Phys. Lett. 207, 414 (1993); R. J. Rico, T. J. Lee, and M. Head-Gordon, ibid. 218, 139 (1994).
13. J. F. Stanton and J. Gauss, J. Chem. Phys. 101, 8938 (1994).
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15. FSMRCC has been extended by Hughes and Kaldor [S. R. Hughes and U. Kaldor, Chem. Phys. Lett. 204, 339 (1993)] to the full CCSDT level [J. Noga and R. J. Bartlett, J. Chem. Phys. 86, 7041 (1987)]. Their work is primarily targeted towards final states that differ in occupation number by as many as six electrons from the reference state, but it has also been used to calculate ionization potentials and electron affinities, specific realizations of FSMRCC for which it is equivalent to EOM-CC. FSMRCC based on CCSDT is a more theoretically complete method than those used in this work, and is among the most sophisticated methods ever used for these calculations. In general, Hughes and Kaldor note improved results when triple excitations are included [S. R. Hughes and U. Kaldor, Int. J. Quantum Chem. 55, 127 (1995)], but examples have been found in which significant degradation of accuracy is found - electron affinities of the halogen atoms when calculated as ionization potentials of the anion [S. R. Hughes and U. Kaldor, J. Chem. Phys. 99, 6773 (1993)]. The reasons for this behavior are unclear, although qualitatively similar features are found in preliminary calculations on fluorine using the methods studied here. In this case, it seems that CCSD-based results are indeed superior to those obtained with the triples-corrected approaches, and that the latter appear to overestimate the effects of 2hp determinants in the final state description [J. F. Stanton and J. Gauss (unpublished research)].
16. FSMRCC has been extended by Hughes and Kaldor [S. R. Hughes and U. Kaldor, Chem. Phys. Lett. 204, 339 (1993)] to the full CCSDT level [J. Noga and R. J. Bartlett, J. Chem. Phys. 86, 7041 (1987)]. Their work is primarily targeted towards final states that differ in occupation number by as many as six electrons from the reference state, but it has also been used to calculate ionization potentials and electron affinities, specific realizations of FSMRCC for which it is equivalent to EOM-CC. FSMRCC based on CCSDT is a more theoretically complete method than those used in this work, and is among the most sophisticated methods ever used for these calculations. In general, Hughes and Kaldor note improved results when triple excitations are included [S. R. Hughes and U. Kaldor, Int. J. Quantum Chem. 55, 127 (1995)], but examples have been found in which significant degradation of accuracy is found - electron affinities of the halogen atoms when calculated as ionization potentials of the anion [S. R. Hughes and U. Kaldor, J. Chem. Phys. 99, 6773 (1993)]. The reasons for this behavior are unclear, although qualitatively similar features are found in preliminary calculations on fluorine using the methods studied here. In this case, it seems that CCSD-based results are indeed superior to those obtained with the triples-corrected approaches, and that the latter appear to overestimate the effects of 2hp determinants in the final state description [J. F. Stanton and J. Gauss (unpublished research)].
17. FSMRCC has been extended by Hughes and Kaldor [S. R. Hughes and U. Kaldor, Chem. Phys. Lett. 204, 339 (1993)] to the full CCSDT level [J. Noga and R. J. Bartlett, J. Chem. Phys. 86, 7041 (1987)]. Their work is primarily targeted towards final states that differ in occupation number by as many as six electrons from the reference state, but it has also been used to calculate ionization potentials and electron affinities, specific realizations of FSMRCC for which it is equivalent to EOM-CC. FSMRCC based on CCSDT is a more theoretically complete method than those used in this work, and is among the most sophisticated methods ever used for these calculations. In general, Hughes and Kaldor note improved results when triple excitations are included [S. R. Hughes and U. Kaldor, Int. J. Quantum Chem. 55, 127 (1995)], but examples have been found in which significant degradation of accuracy is found - electron affinities of the halogen atoms when calculated as ionization potentials of the anion [S. R. Hughes and U. Kaldor, J. Chem. Phys. 99, 6773 (1993)]. The reasons for this behavior are unclear, although qualitatively similar features are found in preliminary calculations on fluorine using the methods studied here. In this case, it seems that CCSD-based results are indeed superior to those obtained with the triples-corrected approaches, and that the latter appear to overestimate the effects of 2hp determinants in the final state description [J. F. Stanton and J. Gauss (unpublished research)].
18. FSMRCC has been extended by Hughes and Kaldor [S. R. Hughes and U. Kaldor, Chem. Phys. Lett. 204, 339 (1993)] to the full CCSDT level [J. Noga and R. J. Bartlett, J. Chem. Phys. 86, 7041 (1987)]. Their work is primarily targeted towards final states that differ in occupation number by as many as six electrons from the reference state, but it has also been used to calculate ionization potentials and electron affinities, specific realizations of FSMRCC for which it is equivalent to EOM-CC. FSMRCC based on CCSDT is a more theoretically complete method than those used in this work, and is among the most sophisticated methods ever used for these calculations. In general, Hughes and Kaldor note improved results when triple excitations are included [S. R. Hughes and U. Kaldor, Int. J. Quantum Chem. 55, 127 (1995)], but examples have been found in which significant degradation of accuracy is found - electron affinities of the halogen atoms when calculated as ionization potentials of the anion [S. R. Hughes and U. Kaldor, J. Chem. Phys. 99, 6773 (1993)]. The reasons for this behavior are unclear, although qualitatively similar features are found in preliminary calculations on fluorine using the methods studied here. In this case, it seems that CCSD-based results are indeed superior to those obtained with the triples-corrected approaches, and that the latter appear to overestimate the effects of 2hp determinants in the final state description [J. F. Stanton and J. Gauss (unpublished research)].
19. FSMRCC has been extended by Hughes and Kaldor [S. R. Hughes and U. Kaldor, Chem. Phys. Lett. 204, 339 (1993)] to the full CCSDT level [J. Noga and R. J. Bartlett, J. Chem. Phys. 86, 7041 (1987)]. Their work is primarily targeted towards final states that differ in occupation number by as many as six electrons from the reference state, but it has also been used to calculate ionization potentials and electron affinities, specific realizations of FSMRCC for which it is equivalent to EOM-CC. FSMRCC based on CCSDT is a more theoretically complete method than those used in this work, and is among the most sophisticated methods ever used for these calculations. In general, Hughes and Kaldor note improved results when triple excitations are included [S. R. Hughes and U. Kaldor, Int. J. Quantum Chem. 55, 127 (1995)], but examples have been found in which significant degradation of accuracy is found - electron affinities of the halogen atoms when calculated as ionization potentials of the anion [S. R. Hughes and U. Kaldor, J. Chem. Phys. 99, 6773 (1993)]. The reasons for this behavior are unclear, although qualitatively similar features are found in preliminary calculations on fluorine using the methods studied here. In this case, it seems that CCSD-based results are indeed superior to those obtained with the triples-corrected approaches, and that the latter appear to overestimate the effects of 2hp determinants in the final state description [J. F. Stanton and J. Gauss (unpublished research)].
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26. -50 is used to describe the "continuum orbital."
27. 2 term in the reference state triples equation), and it will be included in our upcoming comparison of methods for predicting final state properties.
28. 3 vector is not needed during the iterative solution of the eigenvalue problem since all of its effects can be incorporated noniteratively into the two-body part of the operator that is diagonalized.
29. K. P. Huber and G. Herzberg, Constants of Diatomic Molecules, in NIST Chemistry Web-Book, NIST Standard Reference Number 69, edited by W. G. Mallard and P. J. Lindstrom, November 1998. National Institute of Standards and Technology, Gathersburg MD, 20899 (http:// webbook.nist.gov).
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37. See, for example, U. Kaldor, Theor. Chim. Acta 80, 427 (1991).
38. 5 computational dependence.
39. 5 computational dependence.
40. 5 computational dependence.