Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

被引：25

作者：

Jaoul, Arnaud ^{[1
]}

Nocton, Gregory ^{[1
]}

Clavaguera, Carine ^{[2
]}

机构：

[1] Univ Paris Saclay, LCM, CNRS, Ecole Polytech, Route Saclay, F-91128 Palaiseau, France

[2] Univ Paris Saclay, Univ Paris Sud, CNRS, Lab Chim Phys, 15 Ave Jean Perrin, F-91405 Orsay, France

来源：

CHEMPHYSCHEM | 2017年 / 18卷 / 19期

关键词：

density functional calculations; electron transfer; electronic structure; ELF (electron localization function); lanthanides; GENERALIZED-GRADIENT-APPROXIMATION; LONG-RANGE CORRECTION; OF-SPHERES ALGORITHM; BASIS-SETS; ELECTRON LOCALIZATION; MOLECULAR-STRUCTURE; EXCHANGE-ENERGY; HARTREE-FOCK; M06; SUITE; HYBRID;

D O I：

10.1002/cphc.201700629

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The equilibrium between the radical phenanthroline complex Cp*Sm-2(phen) and the coupling product (Cp*Sm-2(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.

引用

页码：2688 / 2696

页数：9

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