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Evaluating f‐Element Bonding from Structure and Thermodynamics
Author(s) -
Minasian Stefan G.,
Krinsky Jamin L.,
Arnold John
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201101447
Subject(s) - ionic bonding , covalent bond , chemical bond , lanthanide , chemistry , interpretation (philosophy) , molecule , steric effects , thermodynamics , actinide , benchmark (surveying) , characterization (materials science) , electronic structure , measure (data warehouse) , character (mathematics) , materials science , computational chemistry , statistical physics , computer science , nanotechnology , mathematics , physics , data mining , ion , stereochemistry , organic chemistry , inorganic chemistry , geometry , geodesy , programming language , geography
The practical goal to measure and understand the thermodynamic properties of molecules and materials containing f‐elements is often achieved through indirect methods. Of the characterization tools available to inorganic chemists, few are more powerful than X‐ray crystallography. Yet for lanthanides and actinides, interpretation of a bond length is a challenging undertaking that involves a complex interplay of steric and electronic forces. In this Concept article, we perform an analysis of selected examples in which structural criteria alone have been used to draw qualitative conclusions about chemical bonding. In other instances for which such an analysis is not valid, thermodynamic information is evaluated side by side with structural data to provide reasonable interpretations of a covalent/ionic mode of bonding. A geometric variation larger than 3 σ is not necessarily correlated to a change in bonding, nor is an increase in bond energy related to a bond with more covalent character. However, careful consideration of thermodynamic information can lead to reasonable interpretations of electronic structure, and may provide a more reliable benchmark for the theoretical methods which can describe f‐elements.