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Lowest Triplet and Singlet States in N-Methylacridone and N,N′-Dimethylquinacridone: Theory and Experiment
- Source :
- The Journal of Physical Chemistry A. 125:8777-8790
- Publication Year :
- 2021
- Publisher :
- American Chemical Society (ACS), 2021.
-
Abstract
- In this work, radical anion photodetachment photoelectron (PD-PE) spectra of N-methylacridone (NM-AC) and N,N'-dimethyl-trans-quinacridone (NNM-QAC) are presented, from which we derived electron affinities and transition energies from S0 to the lowest excited triplet and singlet states (T1, T2, and S1). Because in molecules with extended π systems and heteroatoms the state density even in the energy range of the lowest excited electronic states is already high, assignment of most of the spectral structures in the PD-PE spectra was possible only on the basis of theoretical calculations. To this end, adiabatic transition energies including zero-point vibrational energy corrections were determined using a combination of density functional theory, time-dependent density functional theory, and multireference configuration interaction methods. Calculated Franck-Condon spectra proved to be particularly valuable for the assignment of the spectra. Surprisingly, the density of electronically excited states in the low-energy regime is smaller for NNM-QAC than for NM-AC. This is due to the fact that the nπ* energies remain nearly the same in the two molecules whereas the lowest ππ* excited singlet and triplet transitions are strongly red-shifted in going from NM-AC to NNM-QAC.
Details
- ISSN :
- 15205215 and 10895639
- Volume :
- 125
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry A
- Accession number :
- edsair.doi...........c6814f643866fd0d8c58054c5220e558