The calculation of 17O chemical shielding in transition metal oxo complexes. I. Comparison of DFT and ab initio approaches, and mechanisms of relativity-induced shielding

Journal of Chemical Physics

Volumn 106, Issue 22, 1997, Pages 9201-9212

  Kaupp, Martin ^a,b   Malkina, Olga L ^c   Malkin, Vladimir G ^c  

^a MAX PLANCK INSTITUT FÜR FESTKÖRPERFORSCHUNG   (Germany)

^b UNIVERSITY OF STUTTGART   (Germany)

^c INSTITUTE OF CHEMISTRY   (Slovakia)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000765683     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.474053     Document Type: Article

References (82)

1. M. Kaupp, V. G. Malkin, O. L. Malkina, and D. R. Salahub, Chem. Phys. Lett. 235, 382 (1995).
2. M. Kaupp, V. G. Malkin, O. L. Malkina, and D. R. Salahub, J. Am. Chem. Soc. 117, 1851, 8492.
3. M. Kaupp, V. G. Malkin, O. L. Malkina, and D. R. Salahub, Chem. Eur. J. 2, 24 (1996); M. Kaupp, Chem. Ber. 129, 527 (1996); Chem. Eur. J. 2, 348 (1996).
4. M. Kaupp, V. G. Malkin, O. L. Malkina, and D. R. Salahub, Chem. Eur. J. 2, 24 (1996); M. Kaupp, Chem. Ber. 129, 527 (1996); Chem. Eur. J. 2, 348 (1996).
5. M. Kaupp, V. G. Malkin, O. L. Malkina, and D. R. Salahub, Chem. Eur. J. 2, 24 (1996); M. Kaupp, Chem. Ber. 129, 527 (1996); Chem. Eur. J. 2, 348 (1996).
6. Y. Ruiz-Morales, G. Schreckenbach, and T. Ziegler, J. Phys. Chem. 100, 3359 (1996).
7. M. Kaupp, J. Chem. Soc., Chem. Commun. 1996, 1141.
8. M. Kaupp, J. Am. Chem. Soc. 118, 3018 (1996).
9. D. V. Simion and T. S. Sorensen, J. Am. Chem. Soc. 118, 7345 (1996).
10. M. Kaupp, Chem. Ber. 129, 535 (1996).
11. Y. Ruiz-Morales, G. Schreckenbach, and T. Ziegler, Organometallics 15, 3920 (1996).
12. M. Bühl, Chem. Phys. Lett. 267, 251 (1997).
13. B. N. Figgis, R. G. Kidd, and R. S. Nyholm, Proc. Soc. 1962, 469.
14. C. Rodger and N. Sheperd, in NMR and the Periodic Table, edited by R. K. Harris and B. E. Mann (Academic, New York, 1978), pp. 383ff.
15. W. McFarlane and H. C. E. McFarlane, in Multinuclear NMR, edited by J. Mason (Plenum, New York, 1987), pp. 403ff.
16. See, e.g., W. A. Herrmann, F. E. Kühn, and P. W. Roesky, J. Organomet. Chem. 485, 243 (1995); M. S. Reynolds and A. Butler, Inorg. Chem. 35, 2378 (1996); K. F. Miller and R. A. D. Wentworth, ibid. 18, 984 (1979).
17. See, e.g., W. A. Herrmann, F. E. Kühn, and P. W. Roesky, J. Organomet. Chem. 485, 243 (1995); M. S. Reynolds and A. Butler, Inorg. Chem. 35, 2378 (1996); K. F. Miller and R. A. D. Wentworth, ibid. 18, 984 (1979).
18. See, e.g., W. A. Herrmann, F. E. Kühn, and P. W. Roesky, J. Organomet. Chem. 485, 243 (1995); M. S. Reynolds and A. Butler, Inorg. Chem. 35, 2378 (1996); K. F. Miller and R. A. D. Wentworth, ibid. 18, 984 (1979).
19. M. Kaupp (in preparation).
20. J. E. Combariza, M. Barfield, and J. H. Enemark, J. Phys. Chem. 95, 5463 (1991).
21. (a) V. G. Malkin, O. L. Malkina, and D. R. Salahub, Chem. Phys. Lett. 204, 80,87 (1993);
22. (b) G. Schreckenbach and T. Ziegler, J. Phys. Chem. 99, 606 (1995);
23. (c) G. Rauhut, S. Puyear, K. Wolinski, and P. Pulay, ibid. 100, 6310 (1996);
24. (d) J. R. Cheeseman, G. W. Trucks, T. A. Keith, and M. J. Frisch, J. Chem. Phys. 104, 5497 (1996).
25. V. G. Malkin, O. L. Malkina, M. E. Casida, and D. R. Salahub, J. Am. Chem. Soc. 116, 5898 (1994).
26. V. G. Malkin, O. L. Malkina, L. A. Eriksson, and D. R. Salahub, in Modern Density Functional Theory: A Tool for Chemistry, edited by J. M. Seminario and P. Politzer (Elsevier, Amsterdam, 1995), Vol. 2.
27. A current-density functional theory (CDFT, see G. Vignale and M. Rasolt, Phys. Rev. B 37, 10685 (1988); G. Vignale, M. Rasolt, and D. J. W. Geldart, in Advances in Quantum Chemistry, edited by S. B. Trickey, Vol. 21 (Academic, San Diego, 1990) with explicitly current-dependent functionals has recently been implemented for the calculation of NMR chemical shifts by Lee et al. [A. M. Lee, N. C. Handy, and S. M. Colwell, J. Chem. Phys. 103, 10095 (1995)]. Initial results with a local-density type approximation for the current dependency gave only very small contributions from the current-dependent terms to paramagnetic shielding. Recently, a gradient-corrected current-density functional has been suggested [A. D. Becke, Can. J. Chem. 74, 995 (1996)].
28. A current-density functional theory (CDFT, see G. Vignale and M. Rasolt, Phys. Rev. B 37, 10685 (1988); G. Vignale, M. Rasolt, and D. J. W. Geldart, in Advances in Quantum Chemistry, edited by S. B. Trickey, Vol. 21 (Academic, San Diego, 1990) with explicitly current-dependent functionals has recently been implemented for the calculation of NMR chemical shifts by Lee et al. [A. M. Lee, N. C. Handy, and S. M. Colwell, J. Chem. Phys. 103, 10095 (1995)]. Initial results with a local-density type approximation for the current dependency gave only very small contributions from the current-dependent terms to paramagnetic shielding. Recently, a gradient-corrected current-density functional has been suggested [A. D. Becke, Can. J. Chem. 74, 995 (1996)].
29. A current-density functional theory (CDFT, see G. Vignale and M. Rasolt, Phys. Rev. B 37, 10685 (1988); G. Vignale, M. Rasolt, and D. J. W. Geldart, in Advances in Quantum Chemistry, edited by S. B. Trickey, Vol. 21 (Academic, San Diego, 1990) with explicitly current-dependent functionals has recently been implemented for the calculation of NMR chemical shifts by Lee et al. [A. M. Lee, N. C. Handy, and S. M. Colwell, J. Chem. Phys. 103, 10095 (1995)]. Initial results with a local-density type approximation for the current dependency gave only very small contributions from the current-dependent terms to paramagnetic shielding. Recently, a gradient-corrected current-density functional has been suggested [A. D. Becke, Can. J. Chem. 74, 995 (1996)].
30. A current-density functional theory (CDFT, see G. Vignale and M. Rasolt, Phys. Rev. B 37, 10685 (1988); G. Vignale, M. Rasolt, and D. J. W. Geldart, in Advances in Quantum Chemistry, edited by S. B. Trickey, Vol. 21 (Academic, San Diego, 1990) with explicitly current-dependent functionals has recently been implemented for the calculation of NMR chemical shifts by Lee et al. [A. M. Lee, N. C. Handy, and S. M. Colwell, J. Chem. Phys. 103, 10095 (1995)]. Initial results with a local-density type approximation for the current dependency gave only very small contributions from the current-dependent terms to paramagnetic shielding. Recently, a gradient-corrected current-density functional has been suggested [A. D. Becke, Can. J. Chem. 74, 995 (1996)].
31. W. Kutzelnigg, U. Fleischer, and M. Schindler, in NMR-Basic Principles and Progress (Springer, Heidelberg, 1990), Vol. 23, pp. 165ff.
32. deMon program: D. R. Salahub, R. Fournier, P. Mlynarski, I. Papai, A. St-Amant, and J. Ushio, in Density Functional Methods in Chemistry, edited by J. Labanowski and J. Andzelm (Springer, New York, 1991); A. St-Amant and D. R. Salahub, Chem. Phys. Lett. 169, 387 (1990).
33. deMon program: D. R. Salahub, R. Fournier, P. Mlynarski, I. Papai, A. St-Amant, and J. Ushio, in Density Functional Methods in Chemistry, edited by J. Labanowski and J. Andzelm (Springer, New York, 1991); A. St-Amant and D. R. Salahub, Chem. Phys. Lett. 169, 387 (1990).
34. J. P. Perdew and Y. Wang, Phys. Rev. B. 45, 13244 (1992); J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eischrig (Akademie, Berlin, 1991); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).
35. J. P. Perdew and Y. Wang, Phys. Rev. B. 45, 13244 (1992); J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eischrig (Akademie, Berlin, 1991); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).
36. J. P. Perdew and Y. Wang, Phys. Rev. B. 45, 13244 (1992); J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eischrig (Akademie, Berlin, 1991); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).
37. A. D. Becke, Phys. Rev. A 38, 3098 (1988).
38. J. P. Perdew, Phys. Rev. B 33, 8822 (1986).
39. S. H. Vosko, L. Wilk, and M. Nusair, Can. J. Chem. 58, 1200 (1980).
40. See, e.g., R. Ditchfield, Mol. Phys. 27, 789 (1974); K. Wolinski, J. F. Hinton, and P. Pulay, J. Am. Chem. Soc. 112, 8251 (1990).
41. See, e.g., R. Ditchfield, Mol. Phys. 27, 789 (1974); K. Wolinski, J. F. Hinton, and P. Pulay, J. Am. Chem. Soc. 112, 8251 (1990).
42. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, GAUSSIAN 94, Revision B.2, Gaussian, Inc., Pittsburgh, PA, 1995.
43. A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
44. C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988); B. Miehlich, A. Savin, H. Stoll, and H. Preuss, Chem. Phys. Lett. 157, 200 (1989).
45. C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988); B. Miehlich, A. Savin, H. Stoll, and H. Preuss, Chem. Phys. Lett. 157, 200 (1989).
46. A. D. Becke, J. Phys. Chem. 98, 1372 (1993).
47. J. Gauss, J. Chem. Phys. 99, 3629 (1993).
48. ACES-II program by J. F. Stanton, J. Gauss, J. D. Watts, W. J. Lauderdale, and R. J. Bartlett, University of Florida, Gainesville, 1994.
49. M. Dolg, U. Wedig, H. Stoll, and H. Preuss, J. Chem. Phys. 86, 866 (1987).
50. D. Andrae, U. Häussermann, M. Dolg, H. Stoll, and H. Preuss, Theor. Chim. Acta 77, 123 (1990).
51. A. W. Ehlers, M. Böhme, S. Dapprich, A. Gobbi, A. Höllwarth, V. Jonas, K. F. Köhler, R. Stegmann, A. Veldkamp, and G. Frenking, Chem. Phys. Lett. 208, 111 (1993).
52. H. J. Partridge, J. Chem. Phys. 87, 6643 (1987); 90, 1043 (1989); H. J. Partridge and K. Faegri, Theor. Chim. Acta 82, 207 (1992).
53. H. J. Partridge, J. Chem. Phys. 87, 6643 (1987); 90, 1043 (1989); H. J. Partridge and K. Faegri, Theor. Chim. Acta 82, 207 (1992).
54. H. J. Partridge, J. Chem. Phys. 87, 6643 (1987); 90, 1043 (1989); H. J. Partridge and K. Faegri, Theor. Chim. Acta 82, 207 (1992).
55. V. G. Malkin, O. L. Malkina, and D. R. Salahub, Chem. Phys. Lett. 261, 335 (1996).
56. D. Sundholm, J. Gauss, and A. Schäfer, J. Chem. Phys. 105, 11051 (1996).
57. A. K. Jameson and C. J. Jameson, Chem. Phys. Lett. 134, 461 (1987).
58. C. Brevard and P. Granger, J. Chem. Phys. 75, 4175 (1981).
59. Data have been obtained from the Inorganic Crystal Structure Data Bank [ICSD, cf. G. Bergerhoff, R. Hundt, P. Sievers, and I. D. Brown, J. Chem. Inf. Comput. Sci. 23, 66 (1983)], update 1995.
60. 4).
61. 4).
62. A. Bergner, M. Dolg, W. Küchle, H. Stoll, and H. Preuss, Mol. Phys. 80, 1431 (1993); d functions have been taken from: Gaussian Basis Sets for Molecular Calculations, edited by S. Huzinaga (Elsevier, New York, 1984).
63. A. Bergner, M. Dolg, W. Küchle, H. Stoll, and H. Preuss, Mol. Phys. 80, 1431 (1993); d functions have been taken from: Gaussian Basis Sets for Molecular Calculations, edited by S. Huzinaga (Elsevier, New York, 1984).
64. J. Gauss and J. F. Stanton, J. Chem. Phys. 104, 2574 (1996).
65. J. Gauss and J. F. Stanton, J. Chem. Phys. 103, 3561 (1995).
66. See, e.g., M. A. Buijse and E. J. Baerends, J. Chem. Phys. 93, 4129 (1990).
67. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963); J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1966), pp. 253ff. This procedure is often erroneously attributed to J. M. Foster, and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
68. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963); J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1966), pp. 253ff. This procedure is often erroneously attributed to J. M. Foster, and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
69. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963); J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1966), pp. 253ff. This procedure is often erroneously attributed to J. M. Foster, and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
70. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963); J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1966), pp. 253ff. This procedure is often erroneously attributed to J. M. Foster, and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
71. J. Pipek and P. G. Mezey, J. Chem. Phys. 90, 4916 (1989).
72. See, e.g., C. J. Jameson, in Nucl. Magn. Resonance, A Specialist Periodical Report, edited by G. A. Webb (The Royal Chemical Society, London, 1997), Vol. 26, Chap. 2.
73. See, e.g., L. Olsson and D. Cremer, J. Chem. Phys. 105, 8995 (1996).
74. M. Bühl, O. L. Malkina, and V. G. Malkin, Helv. Chim. Acta 79, 742 (1996); M. Bühl, Organometallics 16, 261 (1997).
75. M. Bühl, O. L. Malkina, and V. G. Malkin, Helv. Chim. Acta 79, 742 (1996); M. Bühl, Organometallics 16, 261 (1997).
76. Cf., e.g., H. Nakatsuji, in Nuclear Magnetic Shieldings and Molecular Structure, edited by J. A. Tossell (Kluwer, Dordrecht, 1993), pp. 263ff, and references cited.
77. For the BHLYP functional, the gap is still larger by ∼2 eV.
78. 95Mo shielding of oxothiomolybdates, Nakatsuji and co-workers [H. Nakatsuji, M. Sugimoto, and S. Saito, Inorg. Chem. 29, 3095 (1990)] argue instead via higher-energy d→d* excitations (this description appears to be based on a somewhat unconventional assignment of the Mo-X σ-bonding orbitals as metal d orbitals).
79. We have preferred to put the gauge origin at the metal rather than at the oxygen nucleus, as the former choice preserves molecular symmetry and thus the magnetic selection rules. Calculations with the gauge origin at oxygen give very similar shieldings. Alternatively, one could analyze canonical MOs using GIAO methods, but the GAUSSIAN94 program does not provide the corresponding MO analysis.
80. (a) A. E. Reed and F. Weinhold, J. Chem. Phys. 83, 1736 (1985);
81. (b) A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev. 88, 899 (1988).
82. See, e.g., P. Pyykkö, Adv. Quantum Chem. 11, 353 (1978).