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Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes
Author(s) -
Jaoul Arnaud,
Nocton Grégory,
Clavaguéra Carine
Publication year - 2017
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201700629
Subject(s) - lanthanide , atomic orbital , chemistry , covalent bond , monomer , metal , density functional theory , thermodynamics , actinide , computational chemistry , physics , electron , ion , inorganic chemistry , quantum mechanics , organic chemistry , polymer
The equilibrium between the radical phenanthroline complex Cp* 2 Sm(phen) and the coupling product (Cp* 2 Sm(phen)) 2 has been investigated based on quantum chemistry calculations. Topological analyses pointed out that the C−C bond created has a partial covalent character, explaining why both the monomeric and the dimeric forms exist in equilibrium. A large variety of density functionals have been tested to reproduce experimental thermodynamic data for this equilibrium. Finally, the PBE0‐D3 and M06‐2X functionals lead to a good evaluation of the energies and enable a correct description of the ligand to metal charge transfer, both in the 4f and 5d metal orbitals.