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  4. Why are the Interaction Energies of Charge-Transfer Complexes Challenging for DFT?
 
research article

Why are the Interaction Energies of Charge-Transfer Complexes Challenging for DFT?

Steinmann, Stephan  
•
Piemontesi, Cyril  
•
Delachat, Aurore  
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2012
Journal of Chemical Theory and Computation

The description of ground state charge-transfer complexes is highly challenging. Illustrative examples include large overestimations of charge-transfer by local and semi-local density functional approximations as well as inaccurate binding energies. It is demonstrated here that standard density functionals fail to accurately describe interaction energies of charge-transfer complexes not only because of the missing long-range exchange as generally assumed, but also as a result of the neglect of weak interactions. Thus accounting for the missing van der Waals interactions is of key importance. These assertions, based on the evaluation of the extent of stabilization due to dispersion using both DFT coupled with our recent density-dependent dispersion correction (dDsC) and high-level ab initio computations, reflect the imperfect error-cancellation between the overestimation of charge-transfer and the missing long-range interactions. An in-depth energy decomposition analysis of an illustrative series of four small ambidentate molecules (HCN, HNC, HF and ClF) bound together with NF3 provides the main conclusions, which are validated on a prototypical organic charge-transfer complex (i.e., tetrathiafulvalene-tetracyanoquinodimethane, TTF-TCNQ). We establish that the interaction energies for charge-transfer complexes can only be properly described when using well-balanced functionals such as PBE0-dDsC, M06-2X and LC-BOP-LRD.

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Type
research article
DOI
10.1021/ct200930x
Web of Science ID

WOS:000303628400012

Author(s)
Steinmann, Stephan  
Piemontesi, Cyril  
Delachat, Aurore  
Corminboeuf, Clemence  
Date Issued

2012

Published in
Journal of Chemical Theory and Computation
Volume

8

Issue

5

Start page

1629

End page

1640

Subjects

charge transfer complexes

•

TTF-TCNQ

•

density functional theory

•

dispersion

•

self-interaction error

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCMD  
Available on Infoscience
March 28, 2012
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/79068
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