Dual fluorescence of 4-(dimethylamino)-pyridine: a comparative linear response TDDFT versus state-specific CASSCF study including solvent with the PCM model

  1. López-de-Luzuriaga, J.M. 1
  2. Manso, E. 1
  3. Monge, M. 1
  4. Sampedro, D. 1
  1. 1 Universidad de La Rioja

    Universidad de La Rioja

    Logroño, España

    GRID grid.119021.a

Theoretical Chemistry Accounts

ISSN: 1432-881X

Year of publication: 2015

Volume: 134

Issue: 5

Pages: 1-12

Type: Article

Export: RIS
DOI: 10.1007/s00214-015-1659-x SCOPUS: 2-s2.0-84928253346 WoS: 000354555700003 GOOGLE SCHOLAR


Cited by

  • Scopus Cited by: 5 (12-11-2021)

JCR (Journal Impact Factor)

  • Year 2015
  • Journal Impact Factor: 1.806
  • Best Quartile: Q3
  • Area: CHEMISTRY, PHYSICAL Quartile: Q3 Rank in area: 92/144 (Ranking edition: SCIE)

SCImago Journal Rank

  • Year 2015
  • SJR Journal Impact: 0.448
  • Best Quartile: Q3
  • Area: Physical and Theoretical Chemistry Quartile: Q3 Rank in area: 97/165


  • Year 2015
  • CiteScore of the Journal : 3.0
  • Area: Physical and Theoretical Chemistry Percentile: 48


Two different theoretical approaches have been used for the description of the experimentally observed dual luminescence of 4-(dimethylamino)pyridine (DMAP), introducing solvent effects with the polarizable continuum model (PCM), which seems needed to represent the dual fluorescence in polar media. These approaches are the linear response time-dependent density functional theory (TDDFT) and the state-specific complete active space self-consistent field. Both levels of theory represent the expected planar high-energy and the twisted intramolecular charge transfer (ICT) low-energy excited-state structures in the presence of solvent (toluene and acetonitrile). The comparison between both approaches shows that the main distortion of the ICT state is similar for both cases, i.e. twisting to almost 90º of the pyridine ring and the dimethylamino planes, but that other secondary distortions are slightly different. In the case of the TDDFT approach, the geometry optimizations of DMAP in the ground and excited states have been carried out using the conventional linear response approach (LR-PCM) for the solvent inclusion. The LR-PCM and the specific state (SS-PCM) approaches have been used for the prediction of the excitation and emission energies of DMAP in toluene and acetonitrile. The prediction of the emission energies at TDDFT/LR-PCM and CASPT2/PCM (complete active space perturbation theory) levels agrees with the experimental ones. © 2015, Springer-Verlag Berlin Heidelberg.