Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

Arnaud Jaoul; Grégory Nocton; Carine Clavaguéra

doi:10.1002/cphc.201700629

Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

Arnaud Jaoul
, Grégory Nocton
, Carine Clavaguéra

Research output: Contribution to journal › Article › peer-review

Abstract

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

Original language	English
Pages (from-to)	2688-2696
Number of pages	9
Journal	ChemPhysChem
Volume	18
Issue number	19
DOIs	https://doi.org/10.1002/cphc.201700629
Publication status	Published - 6 Oct 2017
Externally published	Yes

Keywords

ELF (electron localization function)
density functional calculations
electron transfer
electronic structure
lanthanides

Access to Document

10.1002/cphc.201700629

Cite this

@article{7c87adf8381d41098c3c9c2af519dc97,

title = "Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes",

abstract = "The equilibrium between the radical phenanthroline complex Cp*2Sm(phen) and the coupling product (Cp*2Sm(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.",

keywords = "ELF (electron localization function), density functional calculations, electron transfer, electronic structure, lanthanides",

author = "Arnaud Jaoul and Gr{\'e}gory Nocton and Carine Clavagu{\'e}ra",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2017",

month = oct,

day = "6",

doi = "10.1002/cphc.201700629",

language = "English",

volume = "18",

pages = "2688--2696",

journal = "ChemPhysChem",

issn = "1439-4235",

number = "19",

}

TY - JOUR

T1 - Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

AU - Jaoul, Arnaud

AU - Nocton, Grégory

AU - Clavaguéra, Carine

PY - 2017/10/6

Y1 - 2017/10/6

N2 - The equilibrium between the radical phenanthroline complex Cp*2Sm(phen) and the coupling product (Cp*2Sm(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.

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

KW - ELF (electron localization function)

KW - density functional calculations

KW - electron transfer

KW - electronic structure

KW - lanthanides

U2 - 10.1002/cphc.201700629

DO - 10.1002/cphc.201700629

M3 - Article

C2 - 28704586

AN - SCOPUS:85030719906

SN - 1439-4235

VL - 18

SP - 2688

EP - 2696

JO - ChemPhysChem

JF - ChemPhysChem

IS - 19

ER -

Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

Abstract

Keywords

Access to Document

Fingerprint

Cite this