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  4. Dispersion-Corrected Energy Decomposition Analysis for Intermolecular Interactions Based on the BLW and dDXDM Methods
 
research article

Dispersion-Corrected Energy Decomposition Analysis for Intermolecular Interactions Based on the BLW and dDXDM Methods

Steinmann, Stephan  
•
Corminboeuf, Clemence  
•
Wu, Wei
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2011
The Journal of Physical Chemistry A

As the simplest variant of the valence bond (VB) theory, the block-localized wave function (BLW) method defines the intermediate electron-localized state self-consistently at the DFT level and can be used to explore the nature of intermolecular interactions in terms of several physically intuitive energy components. Yet, it is unclear how the dispersion interaction affects such a kind of energy decomposition analysis (EDA) as standard density functional approximations neglect the long-range dispersion attractive interactions. Three electron densities corresponding to the initial electron-localized state, optimal electron-localized state, and final electron-delocalized state are involved in the BLW-ED approach; a density-dependent dispersion correction, such as the recently proposed dDXDM approach, can thus uniquely probe the impact of the long-range dispersion effect on EDA results computed at the DFT level. In this paper, we incorporate the dDXDM dispersion corrections into the BLW-ED approach and investigate a range of representative systems such as hydrogen-bonding systems, acid base pairs, and van der Waals complexes. Results show that both the polarization and charge-transfer energies are little affected by the inclusion of the long-range dispersion effect, which thus can be regarded as an independent energy component in EDA.

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Type
research article
DOI
10.1021/jp202560d
Web of Science ID

WOS:000290914500027

Author(s)
Steinmann, Stephan  
Corminboeuf, Clemence  
Wu, Wei
Mo, Yirong
Date Issued

2011

Publisher

American Chemical Society

Published in
The Journal of Physical Chemistry A
Volume

115

Issue

21

Start page

5467

End page

5477

Subjects

density functional theory

•

Dispersion coefficients

•

energy decomposition analysis

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCMD  
Available on Infoscience
May 6, 2011
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/67142
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