title: Computational DFT Study of Ruthenium Tetracarbonyl Polymer.
abstract: Ruthenium tetracarbonyl polymer, [Ru(CO)4]n, a chainlike compound formed by metal-metal interactions, was studied computationally. We first performed tests with selected pure and hybrid GGA density functionals and ab initio methods at HF and MP2 levels of theory to find the most suitable method. Calculated geometries and molecular orbitals were compared to see effectiveness and possible differences of the methods. Hybrid functionals, especially PBE1PBE and MPW1K, were found to produce accurate geometrical parameters compared to the experimental structure, with reasonable computational cost. Bonding in [Ru(CO)4]n chains was studied by calculation of Mayer bond order and theoretical structure factors followed by multipole refinement to get bond critical points according to the quantum theory of atoms in molecules. Ruthenium-ruthenium bonding comparable to that in a Ru3(CO)12 cluster was found with both methods.
authors.affiliation: Department of Chemistry, University of Joensuu, P.O. Box 111, FI-80101 Joensuu, Finland.
authors.forename: Mika
authors.initials: M
authors.lastname: Niskanen
authors.affiliation: Department of Chemistry, University of Joensuu, P.O. Box 111, FI-80101 Joensuu, Finland.
authors.forename: Pipsa
authors.initials: P
authors.lastname: Hirva
authors.affiliation: Department of Chemistry, University of Joensuu, P.O. Box 111, FI-80101 Joensuu, Finland.
authors.forename: Matti
authors.initials: M
authors.lastname: Haukka