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What is the "best" atomic charge model to describe through-space charge-transfer excitations?

Authors
  • Jacquemin, Denis
  • Le Bahers, Tangui
  • Adamo, Carlo
  • Ciofini, Ilaria
Type
Published Article
Journal
Physical Chemistry Chemical Physics
Publisher
The Royal Society of Chemistry
Publication Date
Apr 28, 2012
Volume
14
Issue
16
Pages
5383–5388
Identifiers
DOI: 10.1039/c2cp40261k
PMID: 22426115
Source
Medline
License
Unknown

Abstract

We investigate the efficiency of several partial atomic charge models (Mulliken, Hirshfeld, Bader, Natural, Merz-Kollman and ChelpG) for investigating the through-space charge-transfer in push-pull organic compounds with Time-Dependent Density Functional Theory approaches. The results of these models are compared to benchmark values obtained by determining the difference of total densities between the ground and excited states. Both model push-pull oligomers and two classes of "real-life" organic dyes (indoline and diketopyrrolopyrrole) used as sensitisers in solar cell applications have been considered. Though the difference of dipole moments between the ground and excited states is reproduced by most approaches, no atomic charge model is fully satisfactory for reproducing the distance and amount of charge transferred that are provided by the density picture. Overall, the partitioning schemes fitting the electrostatic potential (e.g. Merz-Kollman) stand as the most consistent compromises in the framework of simulating through-space charge-transfer, whereas the other models tend to yield qualitatively inconsistent values.

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