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Abstract:

We investigate the DFT + U approach as a viable solution to describe the low-lying states of ligated and unligated iron heme complexes. Besides their central role in organometallic chemistry, these compounds represent a paradigmatic case where LDA, GGA, and common hybrid functionals fail to reproduce the experimental magnetic splittings. In particular, the imidazole pentacoordinated heme is incorrectly described as a triplet by all usual DFT flavors. In this study, we show that a U parameter close to 4 eV leads to spin transitions and molecular geometries in quantitative agreement with experiments and that DFT + U represents an appealing tool in the description of iron porphyrin complexes, at a much reduced cost compared to correlated quantum-chemistry methods. The possibility of obtaining the U parameter from first principles is explored through a self-consistent linear-response formulation. We find that this approach, which proved to be successful in other iron systems, produces in this case some overestimation with respect to the optimal values of U. © 2007 American Chemical Society.

Registro:

Documento: Artículo
Título:Simulation of heme using DFT + U: A step toward accurate spin-state energetics
Autor:Scherlis, D.A.; Cococcioni, M.; Sit, P.; Marzari, N.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Pab. II, Buenos Aires (C1428EHA), Argentina
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN 55455, United States
Department of Materials Science and Engineering, Institute for Soldier Nanotechnologies, Massachusetts Institute of Technology, Cambridge, MA 02139, United States
Palabras clave:Complexation; Molecular structure; Nitrogen compounds; Organometallics; Porphyrins; Quantum chemistry; Molecular geometries; Spin transitions; Spin-state energetics; Density functional theory
Año:2007
Volumen:111
Número:25
Página de inicio:7384
Página de fin:7391
DOI: http://dx.doi.org/10.1021/jp0705491
Título revista:Journal of Physical Chemistry B
Título revista abreviado:J Phys Chem B
ISSN:15206106
CODEN:JPCBF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v111_n25_p7384_Scherlis

Referencias:

  • Collman, J.P., Hoard, J.L., Kim, N., Lang, G., Reed, C.A., (1975) J. Am. Chem. Soc, 97, p. 2676
  • Lang, G., Spartalian, K., Reed, C.A., Collman, J.P., (1978) J. Chem. Phys, 69, p. 5424
  • Boyd, P.D.W., Buckingham, A.D., McMecking, R.M., Mitra, S., (1979) Inorg. Chem, 18, p. 3585
  • Goff, H., La Mar, G.N., Reed, C.A., (1977) J. Am. Chem. Soc, 99, p. 3641
  • Mispelter, J., Momenteau, M., Lhoste, J.M., (1980) J, Chem. Phys, 72, p. 1003
  • Scheidt, W.R., Reed, C.A., (1981) Chem. Rev, 81, p. 543
  • Scherlis, D.A., Estrin, D.A., (2002) Int. J. Quantum Chem, 87, p. 158
  • Ghosh, A., Taylor, P.R., (2003) Curr. Opin. Chem. Biol, 7, p. 113
  • Ghosh, A., Taylor, P.R., (2005) J. Chem. Theory Comput, 1, p. 597
  • Deeth, R.J., Fey, N., (2004) J. Comput. Chem, 25, p. 1840
  • Smith, D.M.A., Dupuis, M., Straatsma, T.P., (2005) Mol. Phys, 103, p. 273
  • Harvey, J.N., (2004) Struct. Bonding, 112, p. 151
  • Rovira, C., Kunc, K., Hutter, J., Ballone, P., Parrinello, M., (1997) J. Phys. Chem. A, 101, p. 8914
  • Kozlowski, P.M., Spiro, T.G., Zgierski, M.Z., (2000) J. Phys. Chem. B, 104, p. 10659
  • Liao, M.-S., Scheiner, S., (2002) J. Chem. Phys, 116, p. 3635
  • Choe, Y.-K., Nakajima, T., Hirao, K., Lindh, R., (1999) J. Chem. Phys, 111, p. 3837
  • A 3B state turns out to be 0.12 eV more stable than the lowest singlet state. See: Jensen, K. P.; Roos, B. O.; Ryde, U. J. Inorg. Biochem. 2005, 99, 45; Anisimov, V.I., Zaanen, J., Andersen, O.K., (1991) Phys. Rev. B, 44, p. 943
  • Anisimov, V.I., Solovyev, I.V., Korotin, M.A., Czyzyk, M.T., Sawatzky, G.A., (1993) Phys. Rev. B, 48, p. 16929
  • Solovyev, I.V., Dederichs, P.H., Anisimov, V.I., (1994) Phys. Rev. B, 50, p. 16861
  • Liechtenstein, A.I., Anisimov, V.I., Zaanen, J., (1995) Phys. Rev. B, 52, pp. R5467
  • Dudarev, S.L., Botton, G.A., Savrasov, S.Y., Humphreys, C.J., Sutton, A.P., (1998) Phys. Rev. B, 57, p. 1505
  • Kulik, H.J., Cococcioni, M., Scherlis, D.A., Marzari, N., (2006) Phys. Rev. Lett, 97, p. 103001
  • Rollmann, G., Herper, H.C., Entel, P., (2006) J. Phys. Chem. A, 110, p. 10799
  • Leung, K., Rempe, S.B., Schultz, P.A., Sproviero, E.M., Batista, V.S., Chandross, M.E., Medforth, C.J., (2006) J. Am. Chem. Soc, 128, p. 3659
  • Nolan, M., Parker, S.C., Watson, G.W., (2006) J. Phys. Chem. B, 110, p. 2256
  • Nolan, M., Watson, G.W., (2006) J. Phys. Chem. B, 110, p. 16600
  • Baroni, S., Dal Corso, A., de Gironcoli, S., Giannozzi, P., Cavazzoni, C., Ballabio, G., Scandolo, S., Marzari, N., Kokalj, A, , http://www.quantum- espresso.org
  • Perdew, J.P., Burke, K., Ernzerhof, M., (1996) Phys. Rev. Lett, 77, p. 3865
  • Vanderbilt, D., (1990) Phys. Rev. B, 41, p. 7892
  • Cococcioni, M., de Gironcoli, S., (2005) Phys. Rev. B, 71, p. 35105
  • Marti, M.A., Crespo, A., Capece, L., Boechi, L., Bikiel, D.E., Scherlis, D.A., Estrin, D.A., (2006) J. Inorg. Biochem, 100, p. 761
  • We denote by dπ the linear combinations dxz ± dyz, so dπ can be occupied by up to four electrons; Strayer, L., (1995) Biochemistry, , 4th ed, W. H. Freeman and Company: New York
  • Hoard, J.L., (1975) Porphyrins and Metalloporphyrins, , Smith, K. M, Ed, Elsevier: Amsterdam, New York
  • Reed, C.A., Guiset, F., (1996) J. Am. Chem. Soc, 118, p. 3281
  • Ghosh, A., Persson, B.J., Taylor, P.R., (2003) J. Biol. Inorg. Chem, 8, p. 507
  • Ghosh, A., Gonzalez, E., Vangberg, T., Taylor, P., (2001) J. Porphyrins Phthalocyanines, 5, p. 345
  • Scherlis, D.A., Estrin, D.A., (2001) J. Am. Chem. Soc, 123, p. 8436
  • Momenteau, M., Reed, C.A., (1994) Chem. Rev, 94, p. 659
  • Oertling, W.A., Kean, R.T., Wever, R., Babcock, G.T., (1990) Inorg. Chem, 29, p. 2633
  • Peng, S.-M., Ibers, J.A., (1976) J. Am. Chem. Soc, 98, p. 8032

Citas:

---------- APA ----------
Scherlis, D.A., Cococcioni, M., Sit, P. & Marzari, N. (2007) . Simulation of heme using DFT + U: A step toward accurate spin-state energetics. Journal of Physical Chemistry B, 111(25), 7384-7391.
http://dx.doi.org/10.1021/jp0705491
---------- CHICAGO ----------
Scherlis, D.A., Cococcioni, M., Sit, P., Marzari, N. "Simulation of heme using DFT + U: A step toward accurate spin-state energetics" . Journal of Physical Chemistry B 111, no. 25 (2007) : 7384-7391.
http://dx.doi.org/10.1021/jp0705491
---------- MLA ----------
Scherlis, D.A., Cococcioni, M., Sit, P., Marzari, N. "Simulation of heme using DFT + U: A step toward accurate spin-state energetics" . Journal of Physical Chemistry B, vol. 111, no. 25, 2007, pp. 7384-7391.
http://dx.doi.org/10.1021/jp0705491
---------- VANCOUVER ----------
Scherlis, D.A., Cococcioni, M., Sit, P., Marzari, N. Simulation of heme using DFT + U: A step toward accurate spin-state energetics. J Phys Chem B. 2007;111(25):7384-7391.
http://dx.doi.org/10.1021/jp0705491