A density functional study of EPR parameters for vanadyl complexes containing schiff base ligands

Journal of Physical Chemistry B

Volumn 105, Issue 50, 2001, Pages 12644-12652

  Munzarová, Markéta L ^a,b   Kaupp, Martin ^b  

^a MASARYK UNIVERSITY   (Czech Republic)

^b UNIVERSITY OF WÜRZBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

LIGANDS;

ELECTROMAGNETIC WAVE POLARIZATION; PARAMAGNETIC RESONANCE; PARAMETER ESTIMATION; PROBABILITY DENSITY FUNCTION; SPECTROSCOPIC ANALYSIS; TENSORS;

VANADIUM COMPOUNDS;

EID: 0035924829     PISSN: 10895647     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp015506y     Document Type: Article

References (64)

1. (a) Vilter, H. In Metal Ions in Biological Systems; Sigel, H., Sigel, A., Eds.; Marcel Dekker: New York, 1995; Vol. 31, pp 325-362.
2. (b) Eady, R.R. In Metal Ions in Biological Systems; Sigel, H., Sigel, A., Eds.; Marcel Dekker: New York, 1995; Vol. 31, pp 363-405.
3. (c) Butler, A.; Walker, J.V. Chem. Rev. 1993, 93, 1937-1944.
4. See, e.g., (a) Shechter, Y.; Karlish, S.J.D. Nature 1980, 284, 556-558.
5. (b) Shechter, Y.; Meyerovitch, J.; Farfel, Z.; Sack, J.; Bruck, R.; Bar-Meir, S.; Amir, S.; Degani, H.; Karlish, S.J.D. In Vanadium in Biological Systems; Chasteen, N.D., Ed.; Kluwer Academic Publishers: Dordrecht, The Nederlands, 1990; pp 129-142.
6. (c) Orvig, C.; Thompson, K.H.; Battel, M.; McNeal, J.H. In Metal Ions in Biological Systems; Sigel, H., Sigel, A., Eds.; Marcel Dekker: New York, 1995; Vol. 31, pp 575-594.
7. Crans, D.C. Comments Inorg. Chem. 1994, 16, 35-76.
8. Morky, L.M.; Carrano, C.J. Inorg. Chem. 1993, 32, 6119-6121.
9. Cornman, C.R.; Geiser-Bush, K.M.; Rowley, S.P.; Boyle, P.D. Inorg. Chem. 1997, 36, 6401-6408.
10. Grant, C.V.; Geiser-Bush, K.M.; Cornman, C.R.; Britt, R.D. Inorg. Chem. 1999, 38, 6285-6288.
11. Grant, C.V.; Cope, W.; Ball, J.A.; Maresch, G.G.; Gaffney, B.J.; Fink, W.; Britt, R.D. J. Phys. Chem. B 1999, 103, 10627-10631.
12. Munzarová, M.; Kaupp, M. J. Phys. Chem. A 1999, 103, 9966.
13. Munzarová, M.L.; Kubáček, P.; Kaupp, M. J. Am. Chem. Soc. 2000, 122, 11900-11913.
14. Malkina, O.L.; Vaara, J.; Schimmelpfennig, B.; Munzarová, M.; Malkin, V.G.; Kaupp, M. J. Am. Chem. Soc. 2000, 122, 9206-9218.
15. Collison, D.; Gahan, B.; Mabbs, F. J. Chem. Soc., Dalton Trans. 1987, 111.
16. Abragam, A.; Bleaney, B. Electron Paramagnetic Resonance of Transition Ions; Clarendon Press: Oxford, 1970.
17. Atherton, N.M. Principals of Electron Spin Resonance; Prentice Hall: New York, 1993.
18. Weil, J.A.; Bolton, J.R.; Wertz, J.E. Electron Paramagnetic Resonance: Elementary Theory and Practical Applications; Willey & Sons: New York, 1994.
19. McGarvey, B.R. In Transition Metal Chemistry: A Series of Advances; Carlin, R.L., Ed.; Marcel Dekker: New York, 1966; Vol. 3, pp 89-201.
20. Mabbs, F.E.; Collison, D. Electron Paramagnetic Resonance of d Transition Metal Compounds; Elsevier: Amsterdam, The Netherlands, 1992.
21. Harriman, J.E. Theoretical Foundations of Electron Spin Resonance; Academic Press: New York, 1978.
22. Schreckenbach, G.; Ziegler, T. J. Phys. Chem. A 1997, 101, 3388.
23. Hess, B.A.; Marian, C.M.; Wahlgren, U.; Gropen, O. Chem. Phys. Lett. 1996, 251, 365.
24. The code used is from the following: Schimmelpfennig, B. AMFI, Atomic Spin-Orbit Mean-Field Integral Program; Stockholms Universitet: Stockholm, Sweden 1996.
25. Vosko, S.H.; Wilk, L.; Nusair, M. Can. J. Chem. 1980, 58, 1200.
26. Godbout, N.; Salahub, D.R.; Andzelm, J.; Wimmer, E. Can. J. Chem. 1992, 70, 560.
27. Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Zakrzewski, V.G.; Montgomery, J.A., Jr.; Stratmann, R.E.; Burant, J.C.; Dapprich, S.; Millam, J.M.; Daniels, A.D.; Kudin, K.N.; Strain, M.C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G.A.; Ayala, P.Y.; Cui, Q.; Morokuma, K.; Malick, D.K.; Rabuck, A.D.; Raghavachari, K.; Foresman, J.B.; Cioslowski, J.; Ortiz, J.V.; Stefanov, B.B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R.L.; Fox, D.J.; Keith, T.; Al-Laham, M.A.; Peng, C.Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P.M.W.; Johnson, B.G.; Chen, W.; Wong, M.W.; Andres, J.L.; Head-Gordon, M.; Replogle, E.S.; Pople, J.A. Gaussian 98, revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
28. Becke, A.D. Phys. Rev. A 1988, 38, 3098.
29. Perdew, J.P.; Wang, Y. Phys. Rev. B 1986, 33, 8822; 1986, 34, 7406.
30. Perdew, J.P.; Wang, Y. Phys. Rev. B 1986, 33, 8822; 1986, 34, 7406.
31. Becke, A.D. J. Chem. Phys. 1993, 98, 5648.
32. Becke, A.D. J. Chem. Phys. 1993, 98, 1372.
33. (a) Perdew, J.P. Physica B 1992, 172, 1.
34. (b) Perdew, J.P. In Electronic Structure of Solids '91; Ziesche, P., Eschring, H., Eds.; Akademie Verlag: Berlin, Germany, 1991.
35. (c) Perdew, J.P.; Wang, Y. Phys. Rev. B 1992, 45, 13244.
36. Malkin, V.G.; Malkina, O.L.; Eriksson, L.A.; Salahub, D.R. In Modern Density Functional Theory: A Tool for Chemistry, Vol. 2 of Theoretical and Computational Chemistry; Politzer, P., Seminario, J.M., Eds.; Elsevier: Amsterdam, The Netherlands, 1995; pp 273-347.
37. (a) Salahub, D.R.; Fournier, R.; Mlynarski, P.; Papal, I.; St-Amant, A.; Ushio, J. In Density Functional Methods in Chemistry; Labanowski, J., Andzelm, J., Eds.; Springer: New York, 1991.
38. (b) St-Amant, A.; Salahub, D.R. Chem. Phys. Lett. 1990, 169, 387.
39. Abragam, A.; Pryce, M.H.L. Proc. R. Soc. A 1951, 205, 135.
40. The parameter P depends on the radial wave function of the metal atom in the field of ligands and is usually treated as an adjustable parameter.
41. ij elements.
42. ij is neither symmetrical nor traceless. See ref 14 for a lucid discussion.
43. 1.
44. Formulas 9.248-9.252 of ref 16 have been derived from (9) and (10), restricting the summation over m to the four MOs with the largest d-orbital contributions. In our calculations, we have therefore chosen the four unoccupied MOs with largest computed metal d character.
45. z2.
46. Dolg, M.; Wedig, U.; Stoll, H.; Preuss, H. J. Chem. Phys. 1987, 86, 866.
47. (a) Bergner, A.; Dolg, M.; Küchle, W.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, 1431.
48. (b) d-type polarization functions have been taken from the following: Gaussian Basis Sets for Molecular Calculations; Huzinaga, S., Ed.; Elsevier: New York, 1984.
49. Dunning, T.H.; Hay, H. In Methods of Electronic Structure Theory, Vol. 3 of Modern Theoretical Chemistry; Schaefer, H.F., III., Ed.; Plenum Press: New York, 1977.
50. axial vector. This is not the case for any of the complexes studied here.
51. (a) Bühl, M. Chem. Phys. Lett. 1997, 267, 251.
52. (b) See, also: Godbout, N.; Oldfield, E. J. Am. Chem. Soc. 1997, 119, 8065.
53. Kaupp, M.; Reviakine, R.; Malkina, O.L.; Arbuznikov, A.; Schimmelpfennig, B.; Malkin; V.G. J. Comput. Chem. In press.
54. Carl, P.J.; Isley, S.L.; Larsen, S.C. J. Phys. Chem. A 2001, 105, 4563.
55. van Lenthe, E.; Wormer, P.E.S.; van der Avoird, A. J. Chem. Phys. 1997, 107, 2488.
56. See, e.g.: van Lenthe, E.; van der Avoird, A.; Hagen, W.R.; Reijerse, E.J. J. Phys. Chem. A 2000, 104, 2070, and references therein.
57. Turning this line of reasoning around, from the theoretical orientations of the principal axes, one can estimate the relative sizes of the individual spin-orbit coupling terms.
58. 2.
59. 2 symmetry. For the two other complexes, we observe small deviations from the indicated directions, cf. below.
60. For the definition of the asymmetry (rhombicity) parameter, cf. ref 14, p 116.
61. Belanzoni, P.; Baerends, E.J.; van Asselt, S.; Langewen, P.B. J. Phys. Chem. 1995, 99, 13094.
62. y'x', are zero, because of zero nondiagonal elements of the g tensor (cf. section 2).
63. We note that the asymmetry of the HFC tensor can be influenced also by mixing of the metal 4s orbital into the SOMO, which is symmetry-allowed. This mixing is not considered in the usual interpretations, cf. refs 12, 15, and 16.
64. Patchkovskii, S.; Ziegler T. J. Chem. Phys. 1999, 111, 5730.