DFT tests for group 8 transition metal carbonyl complexes

• Published in: Journal of molecular modeling Vol. 14; no. 3; pp. 171 - 181
• Main Authors: Hirva, Pipsa, Haukka, Matti, Jakonen, Minna, Moreno, M. Andreina
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer-Verlag 01.03.2008
• Subjects: Carbon - chemistry; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Models, Chemical; Models, Molecular; Molecular Medicine; Original Paper; Pyridines - chemistry; Theoretical and Computational Chemistry; Thermodynamics; Transition Elements - chemistry; Transition metals; Density functional calculations; Iron; Ruthenium; Osmium
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-007-0259-7

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. Figure Optimized structure for one of the test molecules, the Ru 3 (CO) 12 cluster, showing the staggered conformation of the carbonyl ligands