Mapping the d-d excited-state manifolds of transition metal β-diiminato-imido complexes. Comparison of density functional theory and CASPT2 energetics

Journal of Physical Chemistry A

Volumn 112, Issue 50, 2008, Pages 12792-12798

  Ghosh, Abhik ^a   Gonzalez, Emmanuel ^a   Tangen, Espen ^a   Roos, Björn O ^b  

^a UNIVERSITY OF TROMSØ   (Norway)

^b LUND UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

COORDINATION REACTIONS; DENSITY FUNCTIONAL THEORY; EXCITED STATES; FUNCTIONS; GROUND STATE; IRON COMPOUNDS; MOLECULAR ORBITALS; PERTURBATION TECHNIQUES; PROBABILITY DENSITY FUNCTION; SPIN DYNAMICS; SULFUR COMPOUNDS; TRANSITION METALS;

AB INITIO; B3LYP HYBRID FUNCTIONAL; DFT CALCULATIONS; DFT METHODS; FUNCTIONALS; IMIDO COMPLEXES; LOW COORDINATIONS; MODEL COMPLEXES; MULTICONFIGURATION; PERTURBATION THEORIES; SPIN STATES; TRIPLET STATES;

COBALT COMPOUNDS;

EID: 58149234955     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp711159h     Document Type: Article

References (52)

1. Mehn, M. P.; Peters, J. C. J. Inorg. Biochem. 2006, 100, 634-643.
2. Dai, X.; Kapoor, P.; Warren, T. H. J. Am. Chem. Soc. 2004, 126, 4798-4799.
3. Jenkins, D. M.; Di Bilio, A. J.; Allen, M. J.; Betley, T.; Peters, J. C. J. Am. Chem. Soc. 2002, 124, 15336-15350.
4. Hu, X.; Meyer, K. J. Am. Chem. Soc. 2004, 126, 16322-16323.
5. Cowley, R. E.; Bontchev, R. P.; Sorrell, J.; Sarraeino, O.; Feng, Y.; Wang, H.; Smith, J. M. J. Am. Chem. Soc. 2007, 129, 2424-2425.
6. Eckart, N. A.; Vaddadi, S.; Stoian, S.; Lachicotte, R. J.; Cundari, T. R.; Holland, P. L. Angew. Chem., Int. Ed. 2006, 45, 6868-6871.
7. Tangen, E.; Conradie, J.; Ghosh, A. J. Chem. Theory Comput. 2007, 3, 448-457.
8. Conradie, J.; Ghosh, A. J. Chem. Theory Comput. 2007, 3, 689-702.
9. Wasbotten, I. H.; Ghosh, A. Inorg. Chem. 2007, 46, 7890-7898.
10. (a) Shay, D. T.; Yap, G. P. A.; Zakharov, L. N.; Rhemgold, A. L.; Theopold, K. H. Angew. Chem., Int. Ed. 2005, 44, 1508-1510.
11. (b) Corrigendum: Shay, D. T.; Yap, G. P. A.; Zakharov, L. N.; Rheingold, A. L.; Theopold, K. H. Angew. Chem. Int. Ed 2006, 45, 7870-7870.
12. Selected studies comparing the performance of different functionals vis-a-vis transition metal spin-state energetics:
13. (a) Ghosh, A.: Persson, B. J.; Taylor, P. R. J. Biol. Inorg. Chem. 2003, 8, 507-511.
14. (b) Swart, M.; Groenhof, A. R.; Ehlers, A. W.; Lammertsma, K. J. Phys. Chem. A 2004, 108, 5479-5483.
15. (c) Swart, M.; Ehlers, A. W.; Lammertsma, K. Mol. Phys. 2004, 102, 2467-2474.
16. (d) Deeth, R. J.; Fey, N. J. Comput. Chem. 2004, 25, 1840-1848.
17. (e) Groenhof, A. R.; Swart, M.; Ehlers, A. W.; Lammertsma, K. J. Phys. Chem. A 2005, 109, 3411-3417.
18. (f) Daku, L. M. L.; Vargas, A.; Hauser, A.; Fouqueau, A.; Casida, M. E. ChemPhysChem 2005, 6, 1393-1410.
19. (g) Ganzenmuller, G.; Berkaine, N.; Fouqueau, A.; Casida, M. E.; Reiher, M. J. Chem. Phys. 2005, 122, Art. No. 234321.
20. (h) De Angelis, F.; Jin, N.; Car, R.; Groves, J. T. Inorg. Chem. 2006, 45, 4268-4276.
21. (i) Vargas, A.; Zerara, M.; Krausz, E.; Hauser, A.; Daku, L. M. L. J. Chem. Theory Comput. 2006, 2, 1342-1359.
22. (j) Rong, C. Y.; Lian, S. X.; Yin, D. L.; Shen, B.; Zhong, A. G.; Bartolotti, L.; Liu, S. B. J. Chem. Phys. 2006, 125, Art. No. 174102.
23. (k) Strickland, N.; Harvey, J. N. J. Phys. Chem. B 2007, 111, 841-852.
24. (l) Conradie, J.; Ghosh, A. J. Phys. Chem. B 2007, 111, 12621-12624.
25. Andersson, K.; Malmqvist, P.-Å.; Roos, B. O. J. Chem. Phys. 1992, 96, 1218-1226.
26. Ghosh, A.; Taylor, P. R. Curt: Opin. Chem. Biol. 2003, 91, 113-124.
27. Harvey, J. N. Struct. Bonding (Berlin) 2004, 112, 151-183.
28. Ghosh, A. J. Biol. Inorg. Chem. 2006, 11, 712-724.
29. (a) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Perderson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671-6687.
30. (b) Erratum. 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.
31. Becke, A. D. Phys. Rev. 1988, A38, 3098.
32. Lee, C.;. Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, 785-789.
33. (a) Perdew, J. P. Phys. Rev. 1986, B33, 8822.
34. (b) Erratum Perdew, J. P. Phys. Rev. 1986, B34, 7406.
35. Watson, M. A.; Handy, N. C.; Cohen, A. J. J. Chem. Phys. 2003, 119, 6475-6481.
36. Stephens, J. Devlin, F. J.; Chabalowski, C. F.: Frisch, M. J. J. Phys. Chem. 1994, 98, 11623-11627.
37. Hertwig, R. H.; Koch, W. Chem. Phys. Lett. 1997, 268, 345-351.
38. 18
39. 2v point group.
40. The ADF program system was obtained from Scientific Computing and Modeling, Amsterdam (http://www.scm.com/). For a description of the methods used in ADF, see: 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.
41. Perdew, J. P.; Burke, K.; Ernzerhof. M. Phys. Rev. Lett. 1996, 77, 3865-3868.
42. Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1997, 7, 8-1396.
43. Reiher, M.;. Salomon, O.; Hess, B. A. Theor. Chem. Acc. 2001, 107, 48.
44. Roos, B. O. Adv. Chem. Phys. 1987, 69, 399-445.
45. Karlström, G.; Lindh, R.; Malmqvist, P.-Å.; Roos, B. O.; Ryde, U.; Veryazov, V.; Widmark, P.-O.; Cossi, M.; Schimmelpfennig, B.; Neogrady, P.; Seijo, L. Comput. Mater. Sci. 2003, 28, 222.
46. The fact that we have used ground-state OLYP geometries in all calculations is worth commenting upon. Several considerations prompted us to choose this course of action. First, geometry optimizations, frequency calculations, and hence estimations of zero-point energy effects are currently not possible at the CASPT2 level. Second, we found in the course of an earlier study of diiminato-imido complexes that the errors in fixed geometry studies, relative to those involving optimization of each excited state, are generally on the order of 0.1 eV. Third, ground-state DFT methods are applicable to only a small subset of states that we have calculated with CASPT2. Overall, the DFT/CASPT2 comparison carried out here is necessarily inexact, but sufficiently accurate, we believe, to be useful.
47. Roos, B. O.; Lindh, R.; Malmqvist, P.-Å.; Veryazov, V.; Widmark, P.-O. J. Phys. Chem. A 2005, 109, 6575.
48. (a) Douglas, M.; Kroll, N. M. Ann. Phys. 1974, 82, 89-155.
49. (b) Hess. B. A. Phys. Rev. 1986, A33, 3742-3748.
50. Andersson, K.; Roos, B. O. Chem. Phys. Lett. 1992, 191, 507-514.
51. Kogut, E.; Wiencko, H. L.; Zhang, L. B.; Cordeau, D. E.; Warren, T. H. J. Am. Chem. Soc. 2005, 127, 11248-11249.
52. Aquilante, F.; Malmqvist, P.-Å.; Pedersen, T. B.; Ghosh, A.; Roos, B. O. J. Chem. Theory Comput. 2008, 4, 694-702.