title: An Ab initio study of the ligand field and charge-transfer transitions of Cr(CN)(6)(3-) and Mo(CN)(6)(3-).
abstract: High-level ab initio calculations on the excited states of Cr(CN)63- and Mo(CN)63- are reported. For the latter complex, a rather large 10 Dq value of 42 000 cm-1 is obtained, reflecting the increased covalency. The lowest lying charge-transfer transitions for both complexes are predicted to be of the type ligand-to-metal, an assignment in agreement with the photochemical behavior of Cr(CN)63-. A good correspondence between the well-known experimental spectrum of the chromium complex and the theoretical CASPT2 excitation energies is found.
authors.affiliation: Department of Chemistry, University of Leuven, Celestijnenlaan 200F, Belgium. marc.hendrickx@chem.kuleuven.ac.be
authors.forename: Marc F A
authors.initials: MF
authors.lastname: Hendrickx
authors.forename: Vladimir S
authors.initials: VS
authors.lastname: Mironov
authors.forename: Liviu F
authors.initials: LF
authors.lastname: Chibotaru
authors.forename: Arnout
authors.initials: A
authors.lastname: Ceulemans