Benchmarking approximate density functional theory for s/d excitation energies in 3d transition metal cations
Nathan E. Schultz
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431
Search for more papers by this authorYan Zhao
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431
Search for more papers by this authorCorresponding Author
Donald G. Truhlar
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431Search for more papers by this authorNathan E. Schultz
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431
Search for more papers by this authorYan Zhao
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431
Search for more papers by this authorCorresponding Author
Donald G. Truhlar
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431Search for more papers by this authorAbstract
Holthausen has recently provided a comprehensive study of density functional theory for calculating the s/d excitation energies of the 3d transition metal cations. This study did not include the effects of scalar relativistic effects, and we show here that the inclusion of scalar relativistic effects significantly alters the conclusions of the study. We find, contrary to the previous study, that local functionals are more accurate for the excitation energies of 3d transition method cations than hybrid functionals. The most accurate functionals, of the 38 tested, are SLYP, PBE, BP86, PBELYP, and PW91. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008
References
- 1 Holthausen, M. C. J Comp Chem 2005, 26, 1505.
- 2 Kohn, W.; Becke, A. D.; Parr, R. G. J Phys Chem 1996, 100, 12974.
- 3 Kohn, W. Rev Mod Phys 1998, 71, 1253.
- 4 Lovell, T.; Stranger, R.; McGrady, J. E. Inorg Chem 2001, 40, 39.
- 5 Reiher, M.; Saloman, O.; Hess, B. A. Theor Chem Acc 2001, 107, 48.
- 6 Calzado, C. J.; Cabrero, J.; Malrieu, J. P.; Cabollol, R. J. J Chem Phys 2002, 116, 3985.
- 7 Saloman, O.; Reiher, M.; Hess, B. A. J Chem Phys 2002, 117, 4729.
- 8 Harvey, J. N.; Poli, R.; Smith, K. M. Coord Chem Rev 2003, 238/239, 347.
- 9 Schoneboom, J. C.; Cohen, S.; Lin, H.; Shaik, S.; Theil, W. J Am Chem Soc 2004, 126, 4017.
- 10 Carreon-Macedo, J.-L.; Harvey, J. N. J Am Chem Soc 2004, 126, 5789.
- 11 Poli, R. J Organomet Chem 2004, 689, 4291.
- 12 Hermann, C.; Neugebauer, J.; Gladysz, J. A.; Reiher, M. 2005, 44, 6174.
- 13 Jenkins, D. M.; Peters, J. C. J Am Chem Soc 2005, 127, 7148.
- 14 Neese, F. J Inorg Biochem 2006, 100, 716.
- 15 Carreon-Macedo, J.-L.; Harvey, J. N. Phys Chem Chem Phys 2006, 8, 93.
- 16
Mehn, M. P.;
Brown, S. D.;
Paine, T. K.;
Brennassel, W. W.;
Cramer, C. J.;
Peters, J. C.;
Que, L. J.
Dalton Trans
2006,
2006,
1347.
10.1039/B509580H Google Scholar
- 17 Rudra, I.; Wu, Q.; Van Voorhis, V. J Chem Phys 2006, 124, 24103.
- 18
Takano, Y.;
Kitigawa, Y.;
Onishi, T.;
Yoshioka, Y.;
Yamaguchi, K.;
Koga, N.;
Iwamura, H.
J Am Chem Soc
2006,
124,
450.
10.1021/ja015967x Google Scholar
- 19 Bachler, V.; Olbrich, G.; Neese, F.; Weighardt, K. Inorg Chem 2002, 41, 4179.
- 20
Lovell, T.;
Torres, R. A.;
Han, W.-G.;
Liu, T.;
Case, D. A.;
Noodleman, L.
Inorg Chem
2002,
41,
5244.
10.1021/ic020474u Google Scholar
- 21 Ghosh, P.; Bill, E.; Weyhermüller, T.; Neese, F.; Wieghardt, K. J Am Chem Soc 2003, 125, 1293.
- 22 Lovell, T.; Himo, F.; Han, W.-G.; Noodleman, L. Coord Chem Rev 2003, 238/239, 211.
- 23 O'Brien, T. A.; Davidson, E. R. Int J Quantum Chem 2003, 92, 294.
- 24 Sinnecker, S.; Neese, F.; Noodleman, L.; Lubitz, W. J Am Chem Soc 2004, 126, 2613.
- 25 Beńard, M.; Berry, J. F.; Co Hon, F. A.; Gaudin, C.; Lopez, X.; Murillo, C. A.; Rohmer, M.-M. Inorg Chem 2006, 45, 3932.
- 26 Schäfer, A.; Huber, C.; Ahlrichs, R. 1994, 100, 5829.
- 27 Becke, A. D. Phys Rev A 1988, 38, 3098.
- 28 Lee, C.; Yang, W.; Parr, R. G. Phys Rev B 1988, 37, 785.
- 29 Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J Phys Chem 1994, 98, 11623.
- 30 Becke, A. D. J Chem Phys 1993, 98, 5648.
- 31 Becke, A. D. J Chem Phys 1993, 98, 1372.
- 32 Balabanov, N. B.; Peterson, K. A. J Chem Phys 2005, 123, 064107.
- 33 Moore, C. E. Atomic Energy Levels; National Bureau of Standards, U.S. Government Printing Office: Washington, DC, 1949.
- 34 Martin, J. M. L.; Sundermann, A.; Fast, P. L.; Truhlar, D. G. J Chem Phys 2000, 113, 1348.
- 35 Martin, R. L.; Hay, P. J. J Chem Phys 1981, 75, 4539.
- 36 Cowan, R. D.; Griffin, D. C. J Opt Soc Am 1976, 66, 1010.
- 37 Čížek, J. Adv Chem Phys 1969, 14, 35.
- 38 Purvis, G. D.; Bartlett, R. J. J Chem Phys 1982, 76, 1910.
- 39
Raghavachari, K.;
Trucks, G. W.;
Pople, J. A.;
Head-Gordon, M.
Chem Phys Lett
1996,
157,
479.
10.1016/S0009-2614(89)87395-6 Google Scholar
- 40 Douglas, M.; Kroll, N. M. Ann Phys (NY) 1974, 82, 89.
- 41 Hess, B. A. Phys Rev A 1989, 39, 6016.
- 42 Adamo, C.; Barone, V. J Chem Phys 1998, 108, 664.
- 43 Perdew, J. P. In Electronic Structure of Solids '91; P. Ziesche; H. Esching, Eds.; Akademie Verlag: Berlin, 1991.
- 44 Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys Rev Lett 1996, 77, 3865.
- 45 Adamo, C.; Barone, V. Chem Phys Lett 1997, 274, 242.
- 46 Adamo, C.; Cossi, M.; Barone, V. THEOCHEM 1999, 493, 145.
- 47 Slater, J. C. Quantum Theory of Molecules and Solids; McGraw-Hill: New York, 1974.
- 48 Perdew, J. P. Phys Rev B 1986, 33, 8822.
- 49 Perdew, J. P.; Wang, Y. Phys Rev B 1992, 98, 1372.
- 50 Schultz, N. E.; Zhao, Y.; Truhlar, D. G. J Phys Chem A 2005, 109, 4388.
- 51 Schultz, N. E.; Zhao, Y.; Truhlar, D. G. J Phys Chem A 2005, 109, 11127.
- 52 Krauss, M.; Stevens, W. J. Annu Rev Phys Chem 1984, 35, 357.
- 53 Schultz, N. E.; Gherman, B. F.; Cramer, C. J.; Truhlar, D. G. J Phys Chem A 2006, 110, 24030.
