title: On the nature of the lowest triplet excited state of the [Rh 2(1,3-diisocyanopropane)(4)]2+ ion.
abstract: The nature of the ground state and the lowest triplet excited state of the [Rh(2)(1,3-diisocyanopropane)(4)](2+) ion have been investigated by the density functional theory. Two locally stable geometrical conformations are found on the potential energy surfaces of both the ground and excited states, corresponding to the eclipsed and twisted conformations, the eclipsed conformation being more stable and having the shorter Rh-Rh bond length. While the Rh-Rh distances of the two conformations differ by approximately 0.4 A, they shorten to the same value upon excitation ( approximately 3.1 A). The excited state originates from the d(z)()()2 (metal antibonding) to p(z)() (ligand-metal bonding) electronic transition. The Mayer Rh-Rh bond order increases from approximately 0.2 to more than 0.8 upon excitation, while the Rh-C(N) bond order shows a slight decrease. A topological bond path between the Rh atoms is found in both the ground and excited states, while the electron localization function (ELF) indicates weak Rh-Rh covalent bonding for the excited state only.
authors.affiliation: Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, USA.
authors.forename: Irina V
authors.initials: IV
authors.lastname: Novozhilova
authors.forename: Anatoliy V
authors.initials: AV
authors.lastname: Volkov
authors.forename: P
authors.initials: P
authors.lastname: Coppens