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Title: Molecular orbitals for properties and spectroscopies

The description and clarification of spectroscopies and properties goes through ab initio calculations. Wave function based calculations (CASSCF/CASPT2) are particularly appealing since they offer spectroscopic accuracy and means of interpretation. we performed such calculations to elucidate the origin of unusual structural changes and intramolecular electron transfer phenomenon. Based on optimized molecular orbitals and a reading of the multireference wave function, it is suggested that intimate interactions are likely to considerably modify the standard pictures. A so-called PIMA (polarization-induced metalâĹŠarene) interaction similar to the more familiar anion-π interaction is responsible for a significant deviation from sp{sup 3} geometry and an energetic stabilization of 50 kJ/mol in Cr(II) benzyl organometallic complexes. In a similar fashion, it is proposed that the energetic profile of the IVCT (inter valence charge transfer) exhibits strong similarities to the Marcus’ theory, suggesting a response behaviour of the ensemble of electrons as electron transfer occurs in Fe{sup 2+}/Fe{sup 3+} bimetallic compound. The electronic reorganization induced by the IVCT process accounts for 11.8 eV, a very large effect that reduces the transfer energy down to 0.89 eV, in very good agreement with experiments.
Authors:
 [1] ;  [2] ; ; ;  [3]
  1. Laboratoire de Chimie Quantique, Institut de Chimie, Université de Strasbourg, 1 rue Blaise Pascal 67000 Strasbourg-France (France)
  2. Quantum Chemistry and Physical Chemistry Celestijnenlaan 200f, 3001 Heverlee - Belgium (Belgium)
  3. Laboratoire de Chimie de Coordination, Institut de Chimie, Université de Strasbourg, 4 rue Blaise Pascal 67081 Strasbourg-France (France)
Publication Date:
OSTI Identifier:
22499153
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Conference Proceedings; Journal Volume: 1702; Journal Issue: 1; Conference: ICCMSE 2015: International conference of computational methods in sciences and engineering 2015, Athens (Greece), 20-23 Mar 2015; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 74 ATOMIC AND MOLECULAR PHYSICS; ACCURACY; ANIONS; C CODES; ELECTRON TRANSFER; ELECTRONS; ENERGY TRANSFER; EV RANGE 01-10; GEOMETRY; INTERACTIONS; IRON IONS; MOLECULAR ORBITAL METHOD; ORGANOMETALLIC COMPOUNDS; POLARIZATION; SPECTROSCOPY; WAVE FUNCTIONS