DFT tests for group 8 transition metal carbonyl complexes

Abstract

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.

Comparison of Carbazole and Fluorene Donating Effects on the Two‐Photon Absorption and Nitric Oxide Photorelease Capabilities of a Ruthenium–Nitrosyl Complex

“…The B3PW91 functional has been shown to outperform other hybrid functionals (e.g., B3LYP) and pure functionals (e.g., PW91) in numerous cases of ruthenium complexes, especially when back-bonding ligands (like NO) are present. [43,44] The vibrational analyses were performed at the same level of theory to verify that the stationary points correspond to minima on the potential energy surfaces. The UV/Vis electronic spectra were then computed at the CAM-B3LYP/6-31G* level of theory, which was selected for its good efficiency in reproducing experimental transition energies.…”

Density functional theory study of a molecular allosteric switch for 2,2′‐bipyridyl‐3,3′‐15‐crown‐5

“…The standard 6-31G(d) basis set was found to be suitable for most of the ligands. A compromise between the accuracy of the method/basis set and the complexity of the system is normally required in a search for a general purpose method, applicable for wider range of compounds 28 such as W(CO) 4 fragment. So, the SDD (Stuttgart-Dresden) basis function together with the corresponding effective core-potential (ECP) 29 was used for transition-metal tungsten (W) in W(CO) 4 fragment.…”

Isoindole and isomeric heterocyclic donating substituents in ruthenium(II)nitrosyl complexes with large first hyperpolarizabilities and potential two-photon absorption capabilities: a computational approach

“…B3LYP) and pure functionals (e.g. PW91) in numerous cases of ruthenium complexes, especially when back bonding ligands (like NO) are present [26,27].…”