Broken-symmetry DFT spin densities of iron nitrosyls, including roussin's red and black salts: Striking differences between pure and hybrid functionals

Journal of Physical Chemistry B

Volumn 113, Issue 30, 2009, Pages 10540-10547

  Hopmann, Kathrin H ^a   Conradie, Jeanet ^a,b   Ghosh, Abhik ^a  

^a UNIVERSITY OF TROMSØ   (Norway)

^b UNIVERSITY OF THE FREE STATE   (South Africa)

Author keywords

[No Author keywords available]

Indexed keywords

IRON;

BROKEN SYMMETRY; HYBRID EXCHANGE; HYBRID FUNCTIONALS; SPIN COUPLINGS; SPIN DENSITIES;

IRON ALLOYS;

EID: 67651210701     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp904135h     Document Type: Article

References (55)

1. Neese, F. J. Biol. Inorg. Chem. 2006, 11, 702-711.
2. (a) Ghosh, A.; Taylor, P. R. Curr. Opin. Chem. Biol. 2003, 91, 113-124.
3. (b) Ghosh, A. J. Biol. Inorg. Chem. 2006, 11, 671-673.
4. Swart, M. J. Chem. Theory Comput. 2008, 4, 2057-2068.
5. Rinaldo, D.; Harvey, J. N.; Friesner, R. A. J. Chem. Phys. 2008, 129, 164108.
6. Conradie, J.; Ghosh, A. J. Phys. Chem. B 2007, 111, 12621-12624.
7. (a) The Smallest Biomolecules: Diatomics and Their Interactions with Heme Proteins; Ghosh, A., Ed.; Elsevier: Amsterdam, The Netherlands, 2008.
8. (b) Nitric Oxide: Biology and Pathobiology; Ignarro, L., Ed.; Academic: San Diego, CA, 2000.
9. (c) Butler, A.; Nicholson, R. Life, Death and Nitric Oxide; The Royal Society of Chemistry: Cambridge, U.K., 2003.
10. McCleverty, J. A. Chem. Rev. 2004, 104, 403-418.
11. Ghosh, A. Acc. Chem. Res. 2005, 38, 943-954.
12. * electrons: Enemark, J. H.; Feltham, R. D. Coord. Chem. Rev. 1974, 13, 339-406.
13. Velde, G. T.; Bickelhaupt, F. M.; Baerends, E. J.; Guerra, C. F.; Van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, 2001.
14. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision E.01; Gaussian, Inc.: Wallingford, CT, 2004.
15. Handy, N. C.; Cohen, A. J. Mol. Phys. 2001, 99, 403-412.
16. (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
17. (b) Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
18. (c) Becke, A. D. J. Chem. Phys. 1992, 96, 2155-2160.
19. (d) Becke, A. D. J. Chem. Phys. 1992, 97, 9173-9177.
20. (e) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
21. Wayland, B. B.; Olson, L. W. J. Am. Chem. Soc. 1974, 96, 6037-6041.
22. Yoshimura, T. Inorg. Chim. Acta 1982, 57, 99-105.
23. Praneeth, V. K. K.; Näther, C.; Peters, G.; Lehnert, N. Inorg. Chem. 2006, 45, 2795-2811.
24. 2-, see: Szilagyi, R. K.; Metz, M.; Solomon, E. I. J. Phys. Chem. A 2002, 106, 2994-3007.
25. For a study of different functionals vis-á-vis metal-ligand covalence in Fe-S clusters, see: Szilagyi, R. K.; Winslow, M. A. J. Comput. Chem. 2006, 27, 1385-1397.
26. Pure and hybrid functionals yield significantly different spin densities for chloroiron corroles: (a) Steene, E.; Wondimagegn, T.; Ghosh, A. J. Phys. Chem. B 2001, 105, 11406-11413
27. (addition/correction: J. Phys. Chem. B 2002, 106, 5312-5312).
28. (b) Zakharieva, O.; Schunemann, V.; Gerdan, M.; Licoccia, S.; Cai, S.; Walker, F. A.; Trautwein, A. X. J. Am. Chem. Soc. 2002, 124, 6636-6648.
29. Conradie, J.; Ghosh, A. J. Inorg. Biochem. 2006, 100, 2069-2073.
30. Franz, K. J.; Lippard, S. J. J. Am. Chem. Soc. 1999, 121, 10504-10512.
31. Tangen, E.; Conradie, J.; Ghosh, A. Inorg. Chem. 2005, 44, 8699-8706.
32. Harrop, T. C.; Song, D.; Lippard, S. J. J. Am. Chem. Soc. 2006, 128, 3528-3529.
33. Conradie, J.; Quarless, D. A., Jr.; Hsu, H.-F.; Harrop, T. C.; Lippard, S. J.; Koch, S. A.; Ghosh, A. J. Am. Chem. Soc. 2007, 129, 10446-10456.
34. Harrop, T. C.; Song, D.; Lippard, S. J. J. Inorg. Biochem. 2007, 101, 1730-1738.
35. Tsou, C.-C.; Lu, T.-T.; Liaw, W. F. J. Am. Chem. Soc. 2007, 129, 12626-12627.
36. Ford, P. C.; Wecksler, S. Coord. Chem. Rev. 2005, 249, 1382-1395.
37. The degree of α/β symmetry breaking is so weak for the OLYP functional that it might not have occured at all, were we to use a larger basis set.
38. For additional DFT studies of antiferromagnetic coupling, see, e.g.:
39. (a) Atanasov, M.; Daul, C. A. Chem. Phys. Lett. 2003, 381, 584-591.
40. (b) Cauchy, T.; Ruiz, E.; Jeannin, O.; Nomura, M.; Fourmigué, M. Chem. Eur. J. 2007, 13, 8858-8866.
41. (c) Valero, R.; Costa, R.; Moreira, I. D. P. R.; Truhlar, D. G.; Illas, F. J. Chem. Phys. 2008, 128, Art. No. 114103.
42. Sanina, N. A.; Chuev, I. I.; Aldoshin, S. M.; Ovanesyan, N. S.; Strelets, V. V.; Geleti, Yu. V. Russ. Chem. Bull. 2000, 49, 444-451.
43. 2〉 value.
44. Wang, R.; Camacho-Fernandez, M. A.; Xu, W.; Zhang, J.; Li, L. Dalton Trans. 2009, 777-786.
45. Glidewell, C.; Hannan, M. E.; Hursthouse, M. B.; Johnson, I. L.; Motevalli, M. J. Chem. Res. 1988, 7, 212-213.
46. Thomas, J. T.; Robertson, J. H.; Cox, E. G. Acta Crystallogr. 1958, 11, 599-604.
47. Bourassa, J.; Lee, B.; Bernhard, S.; Schoonover, J.; Ford, P. C. Inorg. Chem. 1999, 38, 5926-5926.
48. Jaworska, M.; Stasicka, Z. J. Mol. Struct. 2006, 785, 68-75.
49. Reiher, M.; Salomon, O.; Hess, B. A. Theor. Chem. Acc. 2001, 107, 48.
50. (a) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671-6687.
51. (b) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Perderson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1993, 48, 4978-4978.
52. Sanina, N. A.; Aldoshin, S. M. Russ. Chem. Bull. Int. Ed. 2004, 53, 2428-2448.
53. Ray, K.; Petrenko, T.; Wieghardt, K.; Neese, F. Dalton Trans. 2007, 1552-1566.
54. Walker, F. A.; Licoccia, S.; Paolesse, R. J. Inorg. Biochem. 2006, 100, 810-837.
55. Roos, B. O.; Veryazov, V.; Conradie, J.; Taylor, P. R.; Ghosh, A. J. Phys. Chem. B 2008, 112, 14099-14102.