Premium
The UV/Vis Spectrum of Potassium Heptacyanovanadate( III ): A Theoretical Multi‐Reference Configuration Interaction Study Combined with Low‐Temperature Experiments
Author(s) -
Schmid Volker,
Linder Rolf,
Marian Christel M.
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500712
Subject(s) - chemistry , configuration interaction , excitation , pentagonal bipyramidal molecular geometry , density functional theory , ligand field theory , electronic structure , substructure , atomic physics , crystallography , computational chemistry , molecule , ion , crystal structure , physics , organic chemistry , structural engineering , engineering , quantum mechanics
The electronic spectrum of K 4 [V(CN) 7 ] has been calculated by means of a combined quantum chemical density functional and multi‐reference configuration interaction scheme. In addition to the states known so far, our calculations predict the existence of two low‐lying triplet electronic states with excitation energies of 13600 and 13700 cm –1 , respectively. Both result from d e ″ 1→ d e ′ 2excitations in the slightly distorted pentagonal‐bipyramidal ligand field. To validate these theoretical results we measured a UV/Vis spectrum at low temperatures. In the wavelength range between 800 and 500 nm we observed a broad band with vibrational substructure (peak positions: 13661, 14450, 15243, 16051, and 16807 cm –1 ). The origin transition at 13661 cm –1 is in excellent agreement with our theoretical predictions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)