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  4. Low Lying ππ* State of Heteroaromatic Molecules: A Challenge for Excited State Methods
 
research article

Low Lying ππ* State of Heteroaromatic Molecules: A Challenge for Excited State Methods

Prlj, Antonio  
•
Sandoval-Salinas, María Eugenia
•
Casanova, David
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2016
Journal of Chemical Theory and Computation

The description of low-lying ππ* states of linear acenes by standard electronic structure methods is known to be challenging. Here, we broaden the framework of this problem by considering a set of fused heteroaromatic rings and demonstrate that standard electronic structure methods do not provide a balanced description of the two (typically) lowest singlet state (La and Lb) excitations. While the Lb state is highly sensitive to correlation effects, La suffers from the same drawbacks as charge transfer excitations. We show that the comparison between CIS/CIS(D) can serve as a diagnostic for detecting the two problematic excited states. Standard TD-DFT and even its spin-flip variant lead to inaccurate excitation energies and interstate gaps, with only a double hybrid functional performing somewhat better. The complication inherent to a balanced description of these states is so important that even CC2 and ADC(2) do not necessarily match the ADC(3) reference.

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Type
research article
DOI
10.1021/acs.jctc.6b00245
Web of Science ID

WOS:000378016000014

Author(s)
Prlj, Antonio  
Sandoval-Salinas, María Eugenia
Casanova, David
Jacquemin, Denis
Corminboeuf, Clémence
Date Issued

2016

Publisher

Amer Chemical Soc

Published in
Journal of Chemical Theory and Computation
Volume

12

Start page

2652

End page

2660

Editorial or Peer reviewed

NON-REVIEWED

Written at

EPFL

EPFL units
LCMD  
Available on Infoscience
May 27, 2016
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/126358
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