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Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2016

Low-Lying pi pi* States of Heteroaromatic Molecules: A Challenge for Excited State Methods

Antonio Prlj
  • Fonction : Auteur
Maria Eugenia Sandoval-Salinas
  • Fonction : Auteur
David Casanova
Clemence Corminboeuf
  • Fonction : Auteur

Résumé

The description of low-lying pi pi* 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 (L-a and L-b) excitations. While the L-b state is highly sensitive to correlation effects, L-a 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.

Domaines

Chimie

Dates et versions

hal-02141559 , version 1 (28-05-2019)

Identifiants

Citer

Antonio Prlj, Maria Eugenia Sandoval-Salinas, David Casanova, Denis Jacquemin, Clemence Corminboeuf. Low-Lying pi pi* States of Heteroaromatic Molecules: A Challenge for Excited State Methods. Journal of Chemical Theory and Computation, 2016, 12 (6), pp.2652-2660. ⟨10.1021/acs.jctc.6b00245⟩. ⟨hal-02141559⟩
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