Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Two-Component Spin-orbit Effective Core Potential Calculations with an All-electron Relativistic Program DIRAC

  • Park, Young-Choon (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Lim, Ivan S. (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Lee, Yoon-Sup (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST))
  • Received : 2011.11.15
  • Accepted : 2011.12.13
  • Published : 2012.03.20
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Abstract

We have implemented two-component spin-orbit relativistic effective core potential (SOREP) methods in an all-electron relativistic program DIRAC. This extends the capacity of the two-component SOREP method to many ground and excited state calculations in a single program. As the test cases, geometries and energies of the small halogen molecules were studied. Several two-component methods are compared by using spin-orbit and scalar relativistic effective core potentials. For the $I_2$ molecule, excitation energies of low-lying excited states agree well with those from corresponding all-electron methods. Efficiencies in SOREP calculations enhanced by using symmetries are also discussed briefly.

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References

  1. Pyykko, P. Chem. Rev. 1988, 88, 563. https://doi.org/10.1021/cr00085a006
  2. Pyykko, P. Relativistic Theory of Atoms and Molecules I, II, and III, Springer-Verlag, Berlin.
  3. Dyall, K. G.; Faegri, K. Relativistic Quantum Chemistry, Oxford.
  4. Schwerdfeger, P., Ed.; Relativistic Electronic Structure Theory (Part 1 and 2), Elsevier.
  5. Lee, S. Y.; Lee, Y. S. J. Comp. Chem. 1992, 13, 595. https://doi.org/10.1002/jcc.540130509
  6. Lee, S. Y.; Lee, Y. S. Chem. Phys. Lett. 1991, 187, 302. https://doi.org/10.1016/0009-2614(91)90430-H
  7. Kim, M. C.; Lee, S. Y.; Lee, Y. S. Chem. Phys. Lett. 1996, 253, 216. https://doi.org/10.1016/0009-2614(96)00262-X
  8. Lee, H. S.; Han, Y. K.; Kim, M. C.; Bae, C. B.; Lee, Y. S. Chem. Phys. Lett. 1998, 293, 97. https://doi.org/10.1016/S0009-2614(98)00760-X
  9. Kim, Y. S.; Lee, S. Y.; Oh, W. S.; Park, B. H.; Han, Y. K.; Park, S. J.; Lee, Y. S. Int. J. Quant. Chem. 1998, 66, 1. https://doi.org/10.1002/(SICI)1097-461X(1998)66:1<1::AID-QUA1>3.0.CO;2-Z
  10. Kim, Y. S.; Lee, Y. S. J. Chem. Phys. 2003, 119, 12169. https://doi.org/10.1063/1.1626542
  11. Aa. Jensen, H. J.; Saue, T.; Visscher L. with contributions from Bakken, V., Eliav, E., Enevoldsen, T., Fleig, T., Fossgaard, O., Helgaker, T., Laerdahl, J., Larsen, C. V., Norman, P., Olsen, J., Pernpointner, M., Pedersen, J. K., Ruud, K., Salek, P., van Stralen, J. N. P., Thyssen, J., Visser, O., Winther. T. Dirac, a relativistic ab initio electronic structure program, Release DIRAC04.0 (2004), (http://dirac.chem.sdu.dk).
  12. Lee, Y. S.; Ermler, W. C.; Pitzer, K. S. J. Chem. Phys. 1977, 67, 5861. https://doi.org/10.1063/1.434793
  13. Weeks, J. D. Rice, S. A. J. Chem. Phys. 1968, 49, 2741 https://doi.org/10.1063/1.1670479
  14. Kahn, L. R.; Goddard, W. A. J. Chem. Phys. 1972, 56, 2685. https://doi.org/10.1063/1.1677597
  15. Ermler, W. C.; Lee, Y. S.; Christiansen, P. A.; Pitzer, K. S. Chem. Phys. Lett. 1981, 81, 70. https://doi.org/10.1016/0009-2614(81)85329-8
  16. Pitzer, R. M.; Winter, N. W. J. Phys Chem. 1988, 92, 3061. https://doi.org/10.1021/j100322a011
  17. Dunning, T. H., Jr. J. Chem. Phys. 1989, 90, 1007. https://doi.org/10.1063/1.456153
  18. Woon, D. E.; Dunning, T. H., Jr. J. Chem. Phys. 1993, 98, 1358. https://doi.org/10.1063/1.464303
  19. Pacios, L. F.; Christiansen, P. A. J. Chem. Phys. 1985, 82, 2664. https://doi.org/10.1063/1.448263
  20. Lee, H. S.; Cho, W. K.; Choi, Y. J.; Lee, Y. S. Chem. Phys. 2005, 311, 121. https://doi.org/10.1016/j.chemphys.2004.09.022
  21. Visscher, L.; Styszynski, J.; Nieuwpoort, W. C. J. Chem. Phys. 1987, 105, 1987.
  22. Huber, K. P.; Herzberg, G. Molecular Spectra and Molecular Structure IV, Van Nostrand Reinhold Company.
  23. Kawaguchi, K. J. Chem. Phys. 1988, 88, 4186. https://doi.org/10.1063/1.453825
  24. Larson, J. W.; McMahon, T. B. Inorg. Chem. 1984, 23, 2029. https://doi.org/10.1021/ic00182a010
  25. Visscher, L.; Lee, T. J.; Dyall, K. D. J. Chem. Phys. 1996, 105, 8769. https://doi.org/10.1063/1.472655
  26. Dyall, K. G. Theor. Chem. Acc. 2002, 108, 335. https://doi.org/10.1007/s00214-002-0388-0
  27. Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200. https://doi.org/10.1139/p80-159
  28. Visscher, L.; Eliav, E.; Kaldor, U. J. Chem. Phys. 2001, 115, 9720. https://doi.org/10.1063/1.1415746
  29. de Jong, W. A.; Visscher, L.; Nieuwpoort, W. C. J. Chem. Phys. 1997, 107, 9046. https://doi.org/10.1063/1.475194
  30. Visser, O.; Visscher, L.; Aerts, P. J. C.; Nieuwpoort, W. C. J. Chem. Phys. 1992, 96, 2910. https://doi.org/10.1063/1.461987
  31. Tellinghuisen, J. J. Chem. Phys. 1973, 58, 2821. https://doi.org/10.1063/1.1679584
  32. Tellinghuisen, J. J. Chem. Phys. 1982, 76, 4736. https://doi.org/10.1063/1.442791

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