DFT tests for group 8 transition metal carbonyl complexes
- 322 Downloads
The applicability of several popular density functionals in predicting the geometrical parameters and energetics of transition metal carbonyl complexes of iron, ruthenium and osmium has been studied. The methods tested include pure GGA functionals (BLYP, BP86, OPBE, HCTH, PBE, VSXC) and hybrid GGA functionals (B3PW91, B3LYP, PBE1PBE, MPW1K, B97-2, B1B95, PBE1KCIS). The effect of changing the metal basis set from Huzinaga’s all-electron basis to SDD scECP basis was also studied. The results show, that hybrid functionals are needed in order to describe the back-bonding ability of the carbonyl ligands as well as to deal with metal-metal bonds. The best general performance, when also the computational cost was considered, was obtained with hybrid functionals B3PW91 and PBE1PBE, which therefore provide an efficient tool for solving problems involving large or medium sized transition metal carbonyl compounds.
KeywordsDensity functional calculations Iron Osmium Ruthenium Transition metals
Financial support from the Academy of Finland (P.H., M.J.) is gratefully acknowledged.
- 5.Zhao Y, Truhlar DG (2006) J Chem Phys 124:224105/1–6Google Scholar
- 7.Zhao Y, Truhlar DG (2006) J Chem Phys 125:194101/1–18Google Scholar
- 10.Furche F, Perdew JP (2006) J Chem Phys 124:044103/1–27Google Scholar
- 22.Ramirez-Solis A, Poteau R, Vela A, Daudey JP (2005) J Chem Phys 122:164306/1–10Google Scholar
- 24.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, 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 JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann E, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzales C, Pople JA (2004) Gaussian 03, Revision C.02. Gaussian Inc, Wallingford CTGoogle Scholar
- 25.Basis Sets were obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 02/02/06, as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, Washington 99352, USA, and funded by the U.S. Department of Energy. The Pacific Northwest Laboratory is a Multi-Program Laboratory operated by Battelle Memorial Institute for the U.S. Department of Energy under contract DE-AC06-76RLO 1830. Contact Karen Schuchardt for further information. (2007)Google Scholar
- 26.Huzinaga S (ed.) (1984) Gaussian Basis Sets for Molecular Calculations. Physical Sciences Data 16, Elsevier, AmsterdamGoogle Scholar
- 35.Homanen P, Haukka M, Pakkanen TA, Pursiainen J, Laitinen RH Organometallics 15:4081–4084Google Scholar