Performance of TDDFT Vertical Excitation Energies of Core-Substituted Naphthalene Diimides

Ayush K. Narsaria, Julian D. Ruijter, Trevor A. Hamlin, Andreas W. Ehlers, Célia Fonseca Guerra, Koop Lammertsma, F. Matthias Bickelhaupt

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)


We have evaluated the performance of various density functionals, covering generalized gradient approximation (GGA), global hybrid (GH) and range-separated hybrid (RSH), using time dependent density functional theory (TDDFT) for computing vertical excitation energies against experimental absorption maximum (λmax) for a set of 10 different core-substituted naphthalene diimides (cNDI) recorded in dichloromethane. The computed excitation in case of GH PBE0 is most accurate while the trend is most systematic with RSH LCY-BLYP compared to λmax. We highlight the importance of including solvent effects for optimal agreement with the λmax. Increasing the basis set size from TZ2P to QZ4P has a negligible influence on the computed excitation energies. Notably, RSH CAMY-B3LYP gave the least error for charge-transfer excitation. The poorest agreement with λmax is obtained with semi-local GGA functionals. Use of the optimally-tuned RSH LCY-BLYP* is not recommended because of the high computational cost and marginal improvement in results.

Original languageEnglish
Pages (from-to)1448-1455
Number of pages8
JournalJournal of Computational Chemistry
Issue number15
Publication statusPublished - 5 Jun 2020


  • charge-transfer excitations
  • density functional calculations
  • naphthalene diimides
  • solvent effects
  • time-dependent density functional theory

ASJC Scopus subject areas

  • General Chemistry
  • Computational Mathematics


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