Theoretical view on the origin and implications of structural distortions in polyoxometalates

• Published in: Physics procedia 2010, Vol.8, p.94-103
• Main Authors: López, Xavier, Vilà-Nadal, Laia, Aparicio-Anglès, Xavier, Poblet, Josep M.
• Format: Article
• Language: English
• Subjects: Adsorption; DFT; Distortions; NMR; Polyoxometalates; Quantum chemistry
• ISSN: 1875-3892; 1875-3892
• DOI: 10.1016/j.phpro.2010.10.018

Structural features of polyoxometalates (POMs) —versatile inorganic clusters of academic and technological interest— are discussed in the present article. POMs are, in general, very regular structures presenting a high symmetry in most cases. Distortions are, however, important for some electronic and magnetic properties. We herein discuss some particular geometric features that are crucial for the theoretical treatment and comprehension of well-known experimental phenomena. For instance, we have been able to understand and rationalize the geometrical distortions present in molybdenum POMs. Moreover, we can affirm that these geometrical distortions are caused by a pseudo Jahn Teller effect. In what concerns NMR chemical shifts, we present a discussion on the importance of geometry for the correct description of the signals and the key role played by the interatomic distances. Finally, a study on the adsorption of Keggin clusters on silver surfaces shows how the POM structure looses its regular shape to adapt to that new situation.