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research article

The Charge Transfer Problem in Density Functional Theory Calculations of Aqueously Solvated Molecules

Isborn, Christine M.
•
Mar, Brendan D.
•
Curchod, Basile F. E.  
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2013
The Journal of Physical Chemistry B

Recent advances in algorithms and computational hardware have enabled the calculation of excited states with time-dependent density functional theory (TDDFT) for large systems of O(1000) atoms. Unfortunately, the aqueous charge transfer problem in TDDFT (whereby many spuriously low-lying charge transfer excited states are predicted) seems to become more severe as the system size is increased. In this work, we concentrate on the common case where a chromophore is embedded in aqueous solvent. We examine the role of exchange-correlation functionals, basis set effects, ground state geometries, and the treatment of the external environment in order to assess the root cause of this problem. We conclude that the problem rests largely on water molecules at the boundary of a finite cluster model, i.e., "edge waters." We also demonstrate how the TDDFT problem can be related directly to ground state problems. These findings demand caution in the commonly employed strategy that rests on "snapshot" cutout geometries taken from ground state dynamics with molecular mechanics. We also find that the problem is largely ameliorated when the range-separated hybrid functional LC-omega PBEh is used.

  • Details
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Type
research article
DOI
10.1021/jp4058274
Web of Science ID

WOS:000326367000031

Author(s)
Isborn, Christine M.
Mar, Brendan D.
Curchod, Basile F. E.  
Tavernelli, Ivan  
Martinez, Todd J.
Date Issued

2013

Publisher

American Chemical Society

Published in
The Journal of Physical Chemistry B
Volume

117

Issue

40

Start page

12189

End page

12201

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCBC  
Available on Infoscience
December 9, 2013
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/97721
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